From 99fddb80d955f8b9f1293144b615b841f5ae2b7a Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Wed, 11 Feb 2026 11:41:19 +0200 Subject: [PATCH 01/13] added orca_neb to ts adapters --- arc/job/adapter.py | 1 + 1 file changed, 1 insertion(+) diff --git a/arc/job/adapter.py b/arc/job/adapter.py index fbef435827..aecaf065a1 100644 --- a/arc/job/adapter.py +++ b/arc/job/adapter.py @@ -101,6 +101,7 @@ class JobEnum(str, Enum): gcn = 'gcn' # Graph neural network for isomerization, https://doi.org/10.1021/acs.jpclett.0c00500 user = 'user' # user guesses xtb_gsm = 'xtb_gsm' # Double ended growing string method (DE-GSM), [10.1021/ct400319w, 10.1063/1.4804162] via xTB + orca_neb = 'orca_neb' class JobTypeEnum(str, Enum): From 55d80cb4160ac91f4de93b779d54bdeab3f16bdf Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Wed, 11 Feb 2026 11:42:40 +0200 Subject: [PATCH 02/13] added orca_neb to settings --- arc/settings/settings.py | 13 ++++++++++++- 1 file changed, 12 insertions(+), 1 deletion(-) diff --git a/arc/settings/settings.py b/arc/settings/settings.py index ea2c90a9cc..2a14fd4a2a 100644 --- a/arc/settings/settings.py +++ b/arc/settings/settings.py @@ -82,13 +82,14 @@ 'xtb_gsm': 'local', 'torchani': 'local', 'openbabel': 'local', + 'orca_neb': 'local', } # Electronic structure software ARC may access (use lowercase): supported_ess = ['cfour', 'gaussian', 'mockter', 'molpro', 'orca', 'qchem', 'terachem', 'onedmin', 'xtb', 'torchani', 'openbabel'] # TS methods to try when appropriate for a reaction (other than user guesses which are always allowed): -ts_adapters = ['heuristics', 'AutoTST', 'GCN', 'xtb_gsm'] +ts_adapters = ['heuristics', 'AutoTST', 'GCN', 'xtb_gsm', 'orca_neb'] # List here job types to execute by default default_job_types = {'conf_opt': True, # defaults to True if not specified @@ -162,6 +163,7 @@ 'molpro': 'input.in', 'onedmin': 'input.in', 'orca': 'input.in', + 'orca_neb': 'input.in', 'qchem': 'input.in', 'terachem': 'input.in', 'xtb': 'input.sh', @@ -174,6 +176,7 @@ 'molpro': 'input.out', 'onedmin': 'output.out', 'orca': 'input.log', + 'orca_neb': 'input.log', 'qchem': 'output.out', 'terachem': 'output.out', 'torchani': 'output.yml', @@ -247,6 +250,14 @@ 'nnodes': 15, } +orca_neb_settings = {'keyword': { + 'interpolation': 'IDPP', + 'nnodes': 15, + 'preopt': 'true', + }, + 'level': 'wb97xd/def2tzvp', + } + valid_chars = "-_[]=.,%s%s" % (string.ascii_letters, string.digits) # A scan with better resolution (lower number here) takes more time to compute, From ec88329653fdd735e76d0133860f25c771035d6e Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 16 Feb 2026 08:42:33 +0200 Subject: [PATCH 03/13] added orca neb --- arc/job/adapters/ts/orca_neb.py | 379 ++++++++++++++++++++++++++++++++ 1 file changed, 379 insertions(+) create mode 100644 arc/job/adapters/ts/orca_neb.py diff --git a/arc/job/adapters/ts/orca_neb.py b/arc/job/adapters/ts/orca_neb.py new file mode 100644 index 0000000000..4aafad84d1 --- /dev/null +++ b/arc/job/adapters/ts/orca_neb.py @@ -0,0 +1,379 @@ +""" +An adapter for executing Orca's Nudged Elastic Band (NEB) jobs. + +Orca NEB: +https://www.faccts.de/docs/orca/6.1/manual/contents/structurereactivity/neb.html +""" + +import datetime +import os +from typing import TYPE_CHECKING, List, Optional, Tuple, Union + +from mako.template import Template + +from arc.common import get_logger +from arc.imports import incore_commands, settings +from arc.job.adapters.common import is_restricted, which +from arc.job.adapters.orca import _format_orca_method, _format_orca_basis +from arc.job.factory import register_job_adapter +from arc.job.local import execute_command +from arc.level import Level +from arc.parser.parser import parse_geometry +from arc.species import TSGuess +from arc.species.converter import xyz_to_xyz_file_format + +from arc.species import ARCSpecies + +if TYPE_CHECKING: + from arc.reaction import ARCReaction + +logger = get_logger() + +input_filenames, output_filenames, servers, submit_filenames, orca_neb_settings = \ + settings['input_filenames'], settings['output_filenames'], settings['servers'], settings['submit_filenames'], \ + settings['orca_neb_settings'] + + +input_template = """ +!${restricted}HF ${method} ${basis} NEB-TS +%%maxcore ${memory} +%%pal nprocs ${cpus} end + +%%neb + Interpolation ${interpolation} + NImages ${nnodes} + PrintLevel 3 + PreOpt ${preopt} + NEB_END_XYZFILE "${abs_path}/product.xyz" +END + +* XYZFILE ${charge} ${multiplicity} ${abs_path}/reactant.xyz +""" + + +from arc.job.adapters.orca import OrcaAdapter + + +class OrcaNEBAdapter(OrcaAdapter): + """ + A class for executing Orca NEB jobs. + + Args: + project (str): The project's name. Used for setting the remote path. + project_directory (str): The path to the local project directory. + job_type (list, str): The job's type, validated against ``JobTypeEnum``. If it's a list, pipe.py will be called. + args (dict, optional): Methods (including troubleshooting) to be used in input files. + Keys are either 'keyword', 'block', or 'trsh', values are dictionaries with values + to be used either as keywords or as blocks in the respective software input file. + If 'trsh' is specified, an action might be taken instead of appending a keyword or a + block to the input file (e.g., change server or change scan resolution). + bath_gas (str, optional): A bath gas. Currently only used in OneDMin to calculate L-J parameters. + checkfile (str, optional): The path to a previous Gaussian checkfile to be used in the current job. + conformer (int, optional): Conformer number if optimizing conformers. + constraints (list, optional): A list of constraints to use during an optimization or scan. + cpu_cores (int, optional): The total number of cpu cores requested for a job. + dihedral_increment (float, optional): The degrees increment to use when scanning dihedrals of TS guesses. + dihedrals (List[float], optional): The dihedral angels corresponding to self.torsions. + directed_scan_type (str, optional): The type of the directed scan. + ess_settings (dict, optional): A dictionary of available ESS and a corresponding server list. + ess_trsh_methods (List[str], optional): A list of troubleshooting methods already tried out. + execution_type (str, optional): The execution type, 'incore', 'queue', or 'pipe'. + fine (bool, optional): Whether to use fine geometry optimization parameters. Default: ``False``. + initial_time (datetime.datetime or str, optional): The time at which this job was initiated. + irc_direction (str, optional): The direction of the IRC job (`forward` or `reverse`). + job_id (int, optional): The job's ID determined by the server. + job_memory_gb (int, optional): The total job allocated memory in GB (14 by default). + job_name (str, optional): The job's name (e.g., 'opt_a103'). + job_num (int, optional): Used as the entry number in the database, as well as in ``job_name``. + job_server_name (str, optional): Job's name on the server (e.g., 'a103'). + job_status (list, optional): The job's server and ESS statuses. + level (Level, optional): The level of theory to use. + max_job_time (float, optional): The maximal allowed job time on the server in hours (can be fractional). + run_multi_species (bool, optional): Whether to run a job for multiple species in the same input file. + reactions (List[ARCReaction], optional): Entries are ARCReaction instances, used for TS search methods. + rotor_index (int, optional): The 0-indexed rotor number (key) in the species.rotors_dict dictionary. + server (str): The server to run on. + server_nodes (list, optional): The nodes this job was previously submitted to. + species (List[ARCSpecies], optional): Entries are ARCSpecies instances. + Either ``reactions`` or ``species`` must be given. + testing (bool, optional): Whether the object is generated for testing purposes, ``True`` if it is. + times_rerun (int, optional): Number of times this job was re-run with the same arguments (no trsh methods). + torsions (List[List[int]], optional): The 0-indexed atom indices of the torsion(s). + tsg (int, optional): TSGuess number if optimizing TS guesses. + xyz (dict, optional): The 3D coordinates to use. If not give, species.get_xyz() will be used. + """ + + def __init__(self, + project: str, + project_directory: str, + job_type: Union[List[str], str], + args: Optional[dict] = None, + bath_gas: Optional[str] = None, + checkfile: Optional[str] = None, + conformer: Optional[int] = None, + constraints: Optional[List[Tuple[List[int], float]]] = None, + cpu_cores: Optional[str] = None, + dihedral_increment: Optional[float] = None, + dihedrals: Optional[List[float]] = None, + directed_scan_type: Optional[str] = None, + ess_settings: Optional[dict] = None, + ess_trsh_methods: Optional[List[str]] = None, + execution_type: Optional[str] = None, + fine: bool = False, + initial_time: Optional[Union['datetime.datetime', str]] = None, + irc_direction: Optional[str] = None, + job_id: Optional[int] = None, + job_memory_gb: float = 14.0, + job_name: Optional[str] = None, + job_num: Optional[int] = None, + job_server_name: Optional[str] = None, + job_status: Optional[List[Union[dict, str]]] = None, + level: Optional[Level] = None, + max_job_time: Optional[float] = None, + run_multi_species: bool = False, + reactions: Optional[List['ARCReaction']] = None, + rotor_index: Optional[int] = None, + server: Optional[str] = None, + server_nodes: Optional[list] = None, + queue: Optional[str] = None, + attempted_queues: Optional[List[str]] = None, + species: Optional[List['ARCSpecies']] = None, + testing: bool = False, + times_rerun: int = 0, + torsions: Optional[List[List[int]]] = None, + tsg: Optional[int] = None, + xyz: Optional[dict] = None, + ): + + if reactions is None: + raise ValueError('Cannot execute Orca NEB without an ARCReaction object.') + + # For NEB calculations, the 'species' argument to the OrcaAdapter should be the TS species from the reaction. + # OrcaAdapter expects a list of species. + # Ensure that reactions[0].ts_species is set for OrcaAdapter's initialization. + # If not explicitly set, create a dummy one for now, as NEB's purpose is to find a TS. + if reactions and reactions[0].ts_species is None: + # Create a dummy TS species from the reactants (or products). + # This is a temporary placeholder to satisfy OrcaAdapter's species requirement. + # The actual TS geometry will be obtained from the NEB calculation. + if reactions[0].r_species: + reactions[0].ts_species = ARCSpecies(label=f'{reactions[0].label}_TS', + is_ts=True, + charge=reactions[0].charge, + multiplicity=reactions[0].multiplicity, + xyz=reactions[0].r_species[0].get_xyz()) + else: # Fallback if no reactant species either, though this shouldn't happen for a valid reaction + raise ValueError('ARCReaction object must contain reactant species to initialize Orca NEB.') + + level = level or orca_neb_settings.get('level', '') + if not level: + raise ValueError('A level of theory must be specified for Orca NEB jobs, either in the job arguments or in the settings file.') + species_for_super = [reactions[0].ts_species] + self.execution_type = execution_type or 'queue' + super().__init__(project=project, + project_directory=project_directory, + job_type=job_type, + args=args, + bath_gas=bath_gas, + checkfile=checkfile, + conformer=conformer, + constraints=constraints, + cpu_cores=cpu_cores, + dihedral_increment=dihedral_increment, + dihedrals=dihedrals, + directed_scan_type=directed_scan_type, + ess_settings=ess_settings, + ess_trsh_methods=ess_trsh_methods, + execution_type=execution_type, + fine=fine, + initial_time=initial_time, + irc_direction=irc_direction, + job_id=job_id, + job_memory_gb=job_memory_gb, + job_name=job_name, + job_num=job_num, + job_server_name=job_server_name, + job_status=job_status, + level=level, + max_job_time=max_job_time, + run_multi_species=run_multi_species, + reactions=reactions, + rotor_index=rotor_index, + server=server, + server_nodes=server_nodes, + queue=queue, + attempted_queues=attempted_queues, + species=species_for_super, + testing=testing, + times_rerun=times_rerun, + torsions=torsions, + tsg=tsg, + xyz=xyz, + ) + + self.job_adapter = 'orca_neb' + self.url = 'https://www.faccts.de/docs/orca/6.1/manual/contents/structurereactivity/neb.html' + self.command = 'orca' + self.local_path_to_output_file = os.path.join(self.local_path, output_filenames[self.job_adapter]) + + def write_input_file(self) -> None: + """ + Write the input file to execute the job on the server. + """ + input_dict = dict() + + input_dict['restricted'] = 'r' if is_restricted(self) else 'u' + input_dict['method'] = _format_orca_method(self.level.method) + input_dict['basis'] = _format_orca_basis(self.level.basis) + input_dict['memory'] = self.input_file_memory + input_dict['cpus'] = self.cpu_cores + input_dict['charge'] = self.charge + input_dict['multiplicity'] = self.multiplicity + input_dict['abs_path'] = self.local_path + + # NEB specific parameters + neb_settings = orca_neb_settings.get('keyword', {}) + input_dict['interpolation'] = neb_settings.get('interpolation', 'IDPP') + input_dict['nnodes'] = neb_settings.get('nnodes', 15) + input_dict['preopt'] = neb_settings.get('preopt', 'true') + + # Write reactant.xyz and product.xyz + atom_map = self.reactions[0].atom_map + if atom_map is None: + raise ValueError('Cannot write Orca NEB input file without an atom map in the reaction.') + + reactant_xyz = self.reactions[0].get_reactants_xyz(return_format=dict) + product_xyz = self.reactions[0].get_products_xyz(return_format=dict) # This implicitly uses the atom map. + + with open(os.path.join(self.local_path, 'reactant.xyz'), 'w') as f: + f.write(xyz_to_xyz_file_format(reactant_xyz)) + with open(os.path.join(self.local_path, 'product.xyz'), 'w') as f: + f.write(xyz_to_xyz_file_format(product_xyz)) + + # Render and write the NEB input file + with open(os.path.join(self.local_path, input_filenames[self.job_adapter]), 'w') as f: + f.write(Template(input_template).render(**input_dict)) + + + def set_files(self) -> None: + """ + Set files to be uploaded and downloaded. Writes the files if needed. + Modifies the self.files_to_upload and self.files_to_download attributes. + + self.files_to_download is a list of remote paths. + + self.files_to_upload is a list of dictionaries, each with the following keys: + ``'name'``, ``'source'``, ``'make_x'``, ``'local'``, and ``'remote'``. + If ``'source'`` = ``'path'``, then the value in ``'local'`` is treated as a file path. + Else if ``'source'`` = ``'input_files'``, then the value in ``'local'`` will be taken + from the respective entry in inputs.py + If ``'make_x'`` is ``True``, the file will be made executable. + """ + # 1. ** Upload ** + # 1.1. submit file + if self.execution_type != 'incore': + # we need a submit file for single or array jobs (either submitted to local or via SSH) + self.write_submit_script() + self.files_to_upload.append(self.get_file_property_dictionary( + file_name=submit_filenames[servers[self.server]['cluster_soft']])) + # 1.2. input file + if not self.iterate_by: + # if this is not a job array, we need the ESS input file + self.write_input_file() + self.files_to_upload.append(self.get_file_property_dictionary(file_name=input_filenames[self.job_adapter])) + # 1.2.1 reactant.xyz and product.xyz + self.files_to_upload.append(self.get_file_property_dictionary(file_name='reactant.xyz')) + self.files_to_upload.append(self.get_file_property_dictionary(file_name='product.xyz')) + + # 1.3. HDF5 file + if self.iterate_by and os.path.isfile(os.path.join(self.local_path, 'data.hdf5')): + self.files_to_upload.append(self.get_file_property_dictionary(file_name='data.hdf5')) + # 1.4 job.sh + job_sh_dict = self.set_job_shell_file_to_upload() # Set optional job.sh files if relevant. + if job_sh_dict is not None: + self.files_to_upload.append(job_sh_dict) + # 2. ** Download ** + # 2.1. HDF5 file + if self.iterate_by and os.path.isfile(os.path.join(self.local_path, 'data.hdf5')): + self.files_to_download.append(self.get_file_property_dictionary(file_name='data.hdf5')) + else: + # 2.2. log file + self.files_to_download.append(self.get_file_property_dictionary( + file_name=output_filenames[self.job_adapter])) + # 2.3. Hessian file generated by frequency calculations + # The Hessian file is useful when the user would like to project out the rotors + if self.job_type in ['freq', 'optfreq']: + self.files_to_download.append(self.get_file_property_dictionary(file_name='input.hess')) + + def set_additional_file_paths(self) -> None: + """ + Set additional file paths specific for the adapter. + Called from set_file_paths() and extends it. + """ + self.reactant_path = os.path.join(self.local_path, 'reactant.xyz') + self.product_path = os.path.join(self.local_path, 'product.xyz') + + def cleanup_files(self): + """Remove unneeded files after run.""" + files_to_remove = ['reactant.xyz', 'product.xyz', input_filenames[self.job_adapter]] + for file_name in files_to_remove: + file_path = os.path.join(self.local_path, file_name) + if os.path.exists(file_path): + os.remove(file_path) + + def process_run(self): + """ + Process a completed orca-NEB run. + """ + tsg = TSGuess(method='orca_neb', + index=len(self.reactions[0].ts_species.ts_guesses), + success=False, + t0=self.initial_time, + ) + if os.path.isfile(self.local_path_to_output_file): + tsg.initial_xyz = parse_geometry(self.local_path_to_output_file) + tsg.execution_time = self.final_time - self.initial_time + tsg.success = True + self.reactions[0].ts_species.ts_guesses.append(tsg) + + def write_submit_script(self) -> None: + """ + Write a submit script to execute the job. + """ + original_job_adapter = self.job_adapter + self.job_adapter = 'orca' # Temporarily change to 'orca' for submit script lookup + try: + super().write_submit_script() + finally: + self.job_adapter = original_job_adapter # Revert job_adapter + + def set_input_file_memory(self) -> None: + """ + Set the input_file_memory attribute. + """ + super().set_input_file_memory() + + def execute_incore(self): + """ + Execute a job incore. + """ + self.initial_time = self.initial_time if self.initial_time else datetime.datetime.now() + which(self.command, + return_bool=True, + raise_error=True, + raise_msg=f'Please install {self.job_adapter}, see {self.url} for more information.', + ) + self._log_job_execution() + execute_command([f'cd {self.local_path}'] + incore_commands[self.job_adapter], executable='/bin/bash') + self.cleanup_files() + self.final_time = datetime.datetime.now() + self.process_run() + + def execute_queue(self): + """ + Execute a job to the server's queue. + """ + self.legacy_queue_execution() + + +register_job_adapter('orca_neb', OrcaNEBAdapter) From d6dc8f62af1ecc1162f540902e8f888f808e265c Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 10:21:28 +0200 Subject: [PATCH 04/13] added neb_tests --- arc/job/adapters/ts/orca_neb_test.py | 187 +++++++++++++++++++++++++++ 1 file changed, 187 insertions(+) create mode 100644 arc/job/adapters/ts/orca_neb_test.py diff --git a/arc/job/adapters/ts/orca_neb_test.py b/arc/job/adapters/ts/orca_neb_test.py new file mode 100644 index 0000000000..9fee865eda --- /dev/null +++ b/arc/job/adapters/ts/orca_neb_test.py @@ -0,0 +1,187 @@ +#!/usr/bin/env python3 +# encoding: utf-8 + +""" +This module contains unit tests for the arc.job.adapters.ts.orca_neb module. +""" + +import os +import shutil +import datetime +import unittest +import unittest.mock +import pytest + +from arc.common import ARC_TESTING_PATH +from arc.job.adapters.ts.orca_neb import OrcaNEBAdapter +from arc.level import Level +from arc.reaction import ARCReaction +from arc.species.species import ARCSpecies + + +class TestOrcaNEB(unittest.TestCase): + """ + Contains unit tests for the OrcaNEBAdapter class. + """ + + @classmethod + def setUpClass(cls): + """ + A method that is run before all unit tests in this class. + """ + cls.maxDiff = None + + cls.project_directory = os.path.join(ARC_TESTING_PATH, 'test_OrcaNEBAdapter') + if os.path.exists(cls.project_directory): + shutil.rmtree(cls.project_directory) + os.makedirs(cls.project_directory) + + # Mock objects for both orca_neb and orca/adapter modules + mock_input_filenames = {'orca_neb': 'input.in', 'orca': 'input.in'} + mock_output_filenames = {'orca_neb': 'input.log', 'orca': 'input.log'} + mock_servers = {'local': {'cluster_soft': 'local', 'un': 'user', 'queues': {}}} + mock_submit_filenames = {'local': 'submit.sub'} + mock_orca_neb_settings = {'keyword': {'interpolation': 'IDPP', 'nnodes': 15, 'preopt': 'true'}} + mock_default_job_settings = {'job_total_memory_gb': 14, 'job_cpu_cores': 8} + mock_t_max_format = {'local': 'hours'} + mock_submit_scripts = {'local': {'orca': 'mock submit script content'}} + + # 1. Mock settings in orca_neb module + cls.settings_patcher = unittest.mock.patch('arc.job.adapters.ts.orca_neb.settings', { + 'input_filenames': mock_input_filenames, + 'output_filenames': mock_output_filenames, + 'servers': mock_servers, + 'submit_filenames': mock_submit_filenames, + 'orca_neb_settings': mock_orca_neb_settings, + 'default_job_settings': mock_default_job_settings + }) + cls.mock_settings = cls.settings_patcher.start() + + # 2. Mock settings in orca module (it's imported as OrcaAdapter) + cls.orca_settings_patcher = unittest.mock.patch('arc.job.adapters.orca.settings', { + 'input_filenames': mock_input_filenames, + 'output_filenames': mock_output_filenames, + 'servers': mock_servers, + 'submit_filenames': mock_submit_filenames, + 'default_job_settings': mock_default_job_settings, + 'global_ess_settings': {} + }) + cls.mock_orca_settings = cls.orca_settings_patcher.start() + + # 3. Mock module-level variables in arc.job.adapter and arc.job.adapters.ts.orca_neb's global scope + cls.adapter_servers_patcher = unittest.mock.patch('arc.job.adapter.servers', mock_servers) + cls.mock_adapter_servers = cls.adapter_servers_patcher.start() + + cls.adapter_submit_filenames_patcher = unittest.mock.patch('arc.job.adapter.submit_filenames', mock_submit_filenames) + cls.mock_adapter_submit_filenames = cls.adapter_submit_filenames_patcher.start() + + cls.adapter_submit_scripts_patcher = unittest.mock.patch('arc.job.adapter.submit_scripts', mock_submit_scripts) + cls.mock_adapter_submit_scripts = cls.adapter_submit_scripts_patcher.start() + + cls.adapter_t_max_format_patcher = unittest.mock.patch('arc.job.adapter.t_max_format', mock_t_max_format) + cls.mock_adapter_t_max_format = cls.adapter_t_max_format_patcher.start() + + cls.adapter_output_filenames_patcher = unittest.mock.patch('arc.job.adapter.output_filenames', mock_output_filenames) + cls.mock_adapter_output_filenames = cls.adapter_output_filenames_patcher.start() + + # Also need to mock output_filenames in orca_neb global scope if it was imported as such + cls.orca_neb_output_filenames_patcher = unittest.mock.patch('arc.job.adapters.ts.orca_neb.output_filenames', mock_output_filenames) + cls.mock_orca_neb_output_filenames = cls.orca_neb_output_filenames_patcher.start() + + # 4. Setup species and reaction + cls.r_species = ARCSpecies(label='i-C3H7', smiles='C[CH]C') + cls.p_species = ARCSpecies(label='n-C3H7', smiles='CC[CH2]') + cls.reaction = ARCReaction(r_species=[cls.r_species], + p_species=[cls.p_species]) + + cls.level = Level(method='b3lyp', basis='sto-3g', + args={'keyword': {'scf_convergence': 'tightscf'}}) + + # Initialize the adapter + cls.job = OrcaNEBAdapter(project='test_orca_neb', + job_type='tsg', + project_directory=cls.project_directory, + reactions=[cls.reaction], + level=cls.level, + server='local') + # Ensure remote_path is set for tests + cls.job.remote_path = os.path.join('/some/remote/path', cls.job.project, cls.job.job_type[0], cls.job.job_name) + + def test_task_1_preparation(self): + """ + Task 1: Creating the input files and setting all the files. + """ + # 1. Test set_files + self.job.files_to_upload = list() + self.job.files_to_download = list() + self.job.set_files() + + # Check that files were added to upload/download lists + upload_names = [f['file_name'] for f in self.job.files_to_upload] + self.assertIn('input.in', upload_names) + self.assertIn('reactant.xyz', upload_names) + self.assertIn('product.xyz', upload_names) + + download_names = [f['file_name'] for f in self.job.files_to_download] + self.assertIn('input.log', download_names) + + # 2. Verify files exist on disk + self.assertTrue(os.path.exists(os.path.join(self.job.local_path, 'input.in'))) + self.assertTrue(os.path.exists(os.path.join(self.job.local_path, 'reactant.xyz'))) + self.assertTrue(os.path.exists(os.path.join(self.job.local_path, 'product.xyz'))) + + # Verify input file content partially + with open(os.path.join(self.job.local_path, 'input.in'), 'r') as f: + content = f.read() + self.assertIn('NEB-TS', content) + self.assertIn('reactant.xyz', content) + self.assertIn('product.xyz', content) + + def test_task_2_post_processing(self): + """ + Task 2: Post processing parts. + """ + # Path to the provided log file + log_path = os.path.join(os.path.dirname(os.path.dirname(os.path.dirname(os.path.dirname(__file__)))), + 'testing', 'neb', 'neb_res.out') + + # Ensure the job's output path points to where we will copy the log + output_path = self.job.local_path_to_output_file + os.makedirs(os.path.dirname(output_path), exist_ok=True) + shutil.copy(log_path, output_path) + + self.job.reactions[0].ts_species.ts_guesses = list() + self.job.initial_time = datetime.datetime(2026, 2, 16, 10, 0, 0) + self.job.final_time = datetime.datetime(2026, 2, 16, 10, 15, 42) + + self.job.process_run() + + self.assertEqual(len(self.job.reactions[0].ts_species.ts_guesses), 1) + tsg = self.job.reactions[0].ts_species.ts_guesses[0] + self.assertTrue(tsg.success) + self.assertEqual(tsg.method, 'orca_neb') + self.assertIsNotNone(tsg.initial_xyz) + self.assertEqual(len(tsg.initial_xyz['symbols']), 10) + + # Verify coordinates match the last one in the log + # C -1.406738 -0.055989 0.104836 + self.assertAlmostEqual(tsg.initial_xyz['coords'][0][0], -1.406738, places=5) + + @classmethod + def tearDownClass(cls): + """ + A method that is run ONCE after all unit tests in this class. + """ + cls.settings_patcher.stop() + cls.orca_settings_patcher.stop() + cls.adapter_servers_patcher.stop() + cls.adapter_submit_filenames_patcher.stop() + cls.adapter_submit_scripts_patcher.stop() + cls.adapter_t_max_format_patcher.stop() + cls.adapter_output_filenames_patcher.stop() + cls.orca_neb_output_filenames_patcher.stop() + shutil.rmtree(cls.project_directory, ignore_errors=True) + + +if __name__ == '__main__': + pytest.main([__file__]) From f51b1afa1e405787285037df3aa692467c2b598c Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 10:51:56 +0200 Subject: [PATCH 05/13] added neb to adapters common --- arc/job/adapters/common.py | 48 +++++++++++++++++++------------------- 1 file changed, 24 insertions(+), 24 deletions(-) diff --git a/arc/job/adapters/common.py b/arc/job/adapters/common.py index 8fb331522c..7ad8495713 100644 --- a/arc/job/adapters/common.py +++ b/arc/job/adapters/common.py @@ -29,48 +29,48 @@ ts_adapters_by_rmg_family = {'1+2_Cycloaddition': ['kinbot'], '1,2_Insertion_CO': ['kinbot'], '1,2_Insertion_carbene': ['kinbot'], - '1,2_shiftC': ['gcn', 'xtb_gsm'], - '1,2_shiftS': ['gcn', 'kinbot', 'xtb_gsm'], + '1,2_shiftC': ['gcn', 'xtb_gsm', 'orca_neb'], + '1,2_shiftS': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], '1,3_Insertion_CO2': ['kinbot'], '1,3_Insertion_ROR': ['kinbot'], '1,3_Insertion_RSR': ['kinbot'], - '1,4_Cyclic_birad_scission': ['gcn', 'xtb_gsm'], + '1,4_Cyclic_birad_scission': ['gcn', 'xtb_gsm', 'orca_neb'], '2+2_cycloaddition': ['kinbot'], - '6_membered_central_C-C_shift': ['gcn', 'xtb_gsm'], - 'Concerted_Intra_Diels_alder_monocyclic_1,2_shiftH': ['gcn', 'xtb_gsm'], + '6_membered_central_C-C_shift': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Concerted_Intra_Diels_alder_monocyclic_1,2_shiftH': ['gcn', 'xtb_gsm', 'orca_neb'], 'Cyclic_Ether_Formation': ['kinbot'], - 'Cyclopentadiene_scission': ['gcn', 'xtb_gsm'], + 'Cyclopentadiene_scission': ['gcn', 'xtb_gsm', 'orca_neb'], 'Diels_alder_addition': ['kinbot'], 'H_Abstraction': ['heuristics', 'autotst'], 'carbonyl_based_hydrolysis': ['heuristics'], 'ether_hydrolysis': ['heuristics'], 'nitrile_hydrolysis': ['heuristics'], 'HO2_Elimination_from_PeroxyRadical': ['kinbot'], - 'Intra_2+2_cycloaddition_Cd': ['gcn', 'xtb_gsm'], - 'Intra_5_membered_conjugated_C=C_C=C_addition': ['gcn', 'xtb_gsm'], - 'Intra_Diels_alder_monocyclic': ['gcn', 'kinbot', 'xtb_gsm'], - 'Intra_Disproportionation': ['gcn', 'xtb_gsm'], - 'Intra_ene_reaction': ['gcn', 'kinbot', 'xtb_gsm'], - 'intra_H_migration': ['autotst', 'gcn', 'kinbot', 'xtb_gsm'], - 'intra_NO2_ONO_conversion': ['gcn', 'xtb_gsm'], - 'intra_OH_migration': ['gcn', 'kinbot', 'xtb_gsm'], - 'Intra_RH_Add_Endocyclic': ['gcn', 'kinbot', 'xtb_gsm'], - 'Intra_RH_Add_Exocyclic': ['gcn', 'kinbot', 'xtb_gsm'], - 'Intra_R_Add_Endocyclic': ['gcn', 'kinbot', 'xtb_gsm'], - 'Intra_R_Add_Exo_scission': ['gcn', 'xtb_gsm'], - 'Intra_R_Add_Exocyclic': ['gcn', 'kinbot', 'xtb_gsm'], + 'Intra_2+2_cycloaddition_Cd': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Intra_5_membered_conjugated_C=C_C=C_addition': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Intra_Diels_alder_monocyclic': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Intra_Disproportionation': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Intra_ene_reaction': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'intra_H_migration': ['autotst', 'gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'intra_NO2_ONO_conversion': ['gcn', 'xtb_gsm', 'orca_neb'], + 'intra_OH_migration': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Intra_RH_Add_Endocyclic': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Intra_RH_Add_Exocyclic': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Intra_R_Add_Endocyclic': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Intra_R_Add_Exo_scission': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Intra_R_Add_Exocyclic': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], 'Intra_R_Add_ExoTetCyclic': ['kinbot'], 'Intra_Retro_Diels_alder_bicyclic': ['kinbot'], - 'intra_substitutionCS_isomerization': ['gcn', 'xtb_gsm'], - 'intra_substitutionS_isomerization': ['gcn', 'xtb_gsm'], - 'Ketoenol': ['gcn', 'kinbot', 'xtb_gsm'], - 'Korcek_step1': ['gcn', 'xtb_gsm'], + 'intra_substitutionCS_isomerization': ['gcn', 'xtb_gsm', 'orca_neb'], + 'intra_substitutionS_isomerization': ['gcn', 'xtb_gsm', 'orca_neb'], + 'Ketoenol': ['gcn', 'kinbot', 'xtb_gsm', 'orca_neb'], + 'Korcek_step1': ['gcn', 'xtb_gsm', 'orca_neb'], 'Korcek_step2': ['kinbot'], 'R_Addition_COm': ['kinbot'], 'R_Addition_CSm': ['kinbot'], 'R_Addition_MultipleBond': ['autotst', 'kinbot'], 'Retroene': ['kinbot'], - 'Singlet_Carbene_Intra_Disproportionation': ['gcn', 'xtb_gsm'], + 'Singlet_Carbene_Intra_Disproportionation': ['gcn', 'xtb_gsm', 'orca_neb'], } all_families_ts_adapters = [] From 7c3d6398c36f512f8b3c20d6b4c6391bcb9fea89 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 17:34:38 +0200 Subject: [PATCH 06/13] added neb to init --- arc/job/adapters/ts/__init__.py | 1 + 1 file changed, 1 insertion(+) diff --git a/arc/job/adapters/ts/__init__.py b/arc/job/adapters/ts/__init__.py index 29444e0ed4..5d571e8e80 100644 --- a/arc/job/adapters/ts/__init__.py +++ b/arc/job/adapters/ts/__init__.py @@ -3,3 +3,4 @@ import arc.job.adapters.ts.heuristics import arc.job.adapters.ts.kinbot_ts import arc.job.adapters.ts.xtb_gsm +import arc.job.adapters.ts.orca_neb From 958510abf770d6b455ba7832ccc909b19f454b54 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 17:37:03 +0200 Subject: [PATCH 07/13] added get time from orca --- arc/parser/parser.py | 46 ++++++++++++++++++++++++++++++++++++++++++++ 1 file changed, 46 insertions(+) diff --git a/arc/parser/parser.py b/arc/parser/parser.py index c417f3c2d0..c6469560aa 100644 --- a/arc/parser/parser.py +++ b/arc/parser/parser.py @@ -2,6 +2,7 @@ A module for parsing information from various files. """ +import datetime import os import re from typing import Any, Callable, Dict, List, Optional, Tuple, Type, Union, Match @@ -588,3 +589,48 @@ def parse_active_space(sp_path: str, species: 'ARCSpecies') -> Optional[Dict[str # We should therefore add another active orbital to the 1st irrep. active['occ'][0] += 1 return active + + +def parse_orca_runtime(log_file_path: str) -> Optional[datetime.timedelta]: + """ + Parse the runtime in seconds from an Orca output file. + + Args: + log_file_path (str): The path to the Orca output file. + Returns: Optional[datetime.timedelta] + The runtime in seconds, or ``None`` if it could not be parsed + """ + if not os.path.isfile(log_file_path): + return None + # Read the last 2000 characters to find the runtime + with open(log_file_path, "rb") as f: + try: + f.seek(-2000, os.SEEK_END) + except OSError: + pass # File is smaller than 2kb + content = f.read().decode("utf-8", errors="ignore") + for line in reversed(content.splitlines()): + if "TOTAL RUN TIME:" in line: + # TOTAL RUN TIME: 0 days 0 hours 5 minutes 28 seconds 21 msec + pattern = ( + r"(\d+)\s+days?\s+" + r"(\d+)\s+hours?\s+" + r"(\d+)\s+minutes?\s+" + r"(\d+)\s+seconds?\s+" + r"(\d+)\s+msec" + ) + + match = re.search(pattern, line) + if not match: + raise ValueError("String format not recognized") + + days, hours, minutes, seconds, milliseconds = map(int, match.groups()) + + return datetime.timedelta( + days=days, + hours=hours, + minutes=minutes, + seconds=seconds, + milliseconds=milliseconds + ) + return None From 3724e96ac5206e2c188cff89b5b98d3bd3cdfa9b Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 17:37:36 +0200 Subject: [PATCH 08/13] added support for legacy exe tsg jobs --- arc/scheduler.py | 33 +++++++++++++++++++++++++++++++-- 1 file changed, 31 insertions(+), 2 deletions(-) diff --git a/arc/scheduler.py b/arc/scheduler.py index 0b4ed71762..cd3ffcadaa 100644 --- a/arc/scheduler.py +++ b/arc/scheduler.py @@ -582,9 +582,9 @@ def schedule_jobs(self): if not (job.job_id in self.server_job_ids and job.job_id not in self.completed_incore_jobs): # This is a successfully completed tsg job. It may have resulted in several TSGuesses. self.end_job(job=job, label=label, job_name=job_name) - if job.local_path_to_output_file.endswith('.yml'): + if job.local_path_to_output_file.endswith('.yml') or job.local_path_to_output_file.endswith('.log'): for rxn in job.reactions: - rxn.ts_species.process_completed_tsg_queue_jobs(yml_path=job.local_path_to_output_file) + rxn.ts_species.process_completed_tsg_queue_jobs(path=job.local_path_to_output_file) # Just terminated a tsg job. # Are there additional tsg jobs currently running for this species? for spec_jobs in job_list: @@ -2663,6 +2663,35 @@ def check_sp_job(self, level_of_theory=job.level, ) + def check_tsg_jobs(self, + label: str, + job: 'JobAdapter', + ): + """ + Check that a transition state guess job converged successfully. + + Args: + label (str): The species label. + job (JobAdapter): The single point job object. + """ + print("Checking TS guess job...") + + if job.job_status[1]['status'] == 'done': + self.post_sp_actions(label, + sp_path=os.path.join(job.local_path_to_output_file), + level=job.level, + ) + # Update restart dictionary and save the yaml restart file: + self.save_restart_dict() + if self.species_dict[label].number_of_atoms == 1: + # save the geometry from the sp job for monoatomic species for which no opt/freq jobs will be spawned + self.output[label]['paths']['geo'] = job.local_path_to_output_file + else: + self.troubleshoot_ess(label=label, + job=job, + level_of_theory=job.level, + ) + def post_sp_actions(self, label: str, sp_path: str, From 7f1f52d10305a5fcec31c8751bd741cfac18d36e Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Mon, 23 Feb 2026 17:38:24 +0200 Subject: [PATCH 09/13] added reading tsg objects from log files --- arc/species/species.py | 32 ++++++++++++++++++++++++-------- 1 file changed, 24 insertions(+), 8 deletions(-) diff --git a/arc/species/species.py b/arc/species/species.py index 0fe014d080..46ed0da2db 100644 --- a/arc/species/species.py +++ b/arc/species/species.py @@ -1566,24 +1566,40 @@ def cluster_tsgs(self): cluster_tsgs.append(tsg) self.ts_guesses = cluster_tsgs - def process_completed_tsg_queue_jobs(self, yml_path: str): + def process_completed_tsg_queue_jobs(self, path: str): """ Process YAML files which are the output of running a TS guess job in the queue. Args: - yml_path (str): The path to the output YAML file. + path (str): The path to the output file. """ - if not isinstance(yml_path, str) or not os.path.isfile(yml_path): + if not isinstance(path, str) or not os.path.isfile(path): return None - tsg_list = read_yaml_file(yml_path) - if not isinstance(tsg_list, list) or not all(isinstance(tsg, dict) for tsg in tsg_list): - return None - tsgs = [TSGuess(ts_dict=tsg_dict) for tsg_dict in tsg_list] - for tsg in tsgs: + from arc.parser.parser import parse_orca_runtime + if path.endswith('.log'): + xyz = parse_geometry(path) + time = parse_orca_runtime(path) + tsg = TSGuess(method='orca_neb', + execution_time=time, + success=True, + family=None, + xyz=xyz, + ) if tsg.initial_xyz is not None and not colliding_atoms(tsg.initial_xyz): if tsg.index is None: tsg.index = len(self.ts_guesses) self.ts_guesses.append(tsg) + elif path.endswith('.yml') or path.endswith('.yaml'): + yml_path = path + tsg_list = read_yaml_file(yml_path) + if not isinstance(tsg_list, list) or not all(isinstance(tsg, dict) for tsg in tsg_list): + return None + tsgs = [TSGuess(ts_dict=tsg_dict) for tsg_dict in tsg_list] + for tsg in tsgs: + if tsg.initial_xyz is not None and not colliding_atoms(tsg.initial_xyz): + if tsg.index is None: + tsg.index = len(self.ts_guesses) + self.ts_guesses.append(tsg) self.cluster_tsgs() def mol_from_xyz(self, From f00644b093ce0f477b42b5637fd034ba9d80b166 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Tue, 24 Feb 2026 09:29:41 +0200 Subject: [PATCH 10/13] added test: parse_orca_runtime --- arc/parser/parser_test.py | 9 +++++++++ 1 file changed, 9 insertions(+) diff --git a/arc/parser/parser_test.py b/arc/parser/parser_test.py index 58024666a4..dcc75752e2 100644 --- a/arc/parser/parser_test.py +++ b/arc/parser/parser_test.py @@ -1000,6 +1000,15 @@ def test_parse_active_space(self): xyz="""N 0.0 0.0 0.0""")) self.assertEqual(active, {'e_o': (5, 4), 'occ': [3, 1, 1, 0, 1, 0, 0, 0], 'closed': [1, 0, 0, 0, 0, 0, 0, 0]}) + def test_parse_orca_runtime(self): + """Test the parse_orca_runtime function""" + import datetime + orca_path = os.path.join(ARC_TESTING_PATH, 'freq', 'orca_example_freq.log') + runtime = parser.parse_orca_runtime(log_file_path=orca_path) + self.assertIsInstance(runtime, datetime.timedelta) + # TOTAL RUN TIME: 0 days 0 hours 0 minutes 8 seconds 89 msec + self.assertEqual(runtime.total_seconds(), 8.089) + if __name__ == '__main__': unittest.main(testRunner=unittest.TextTestRunner(verbosity=2)) From 1c26ddc9bfba8c8b4a7da5dcbcd614d5729f52d5 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Tue, 24 Feb 2026 09:54:01 +0200 Subject: [PATCH 11/13] added neb_results for testing --- arc/testing/neb/neb_res.out | 18797 ++++++++++++++++++++++++++++++++++ 1 file changed, 18797 insertions(+) create mode 100644 arc/testing/neb/neb_res.out diff --git a/arc/testing/neb/neb_res.out b/arc/testing/neb/neb_res.out new file mode 100644 index 0000000000..434aa3a3ba --- /dev/null +++ b/arc/testing/neb/neb_res.out @@ -0,0 +1,18797 @@ + + ***************** + * O R C A * + ***************** + + #, + ### + #### + ##### + ###### + ########, + ,,################,,,,, + ,,#################################,, + ,,##########################################,, + ,#########################################, ''#####, + ,#############################################,, '####, + ,##################################################,,,,####, + ,###########'''' ''''############################### + ,#####'' ,,,,##########,,,, '''####''' '#### + ,##' ,,,,###########################,,, '## + ' ,,###'''' '''############,,, + ,,##'' '''############,,,, ,,,,,,###'' + ,#'' '''#######################''' + ' ''''####'''' + ,#######, #######, ,#######, ## + ,#' '#, ## ## ,#' '#, #''# ,####, ,####, + ## ## ## ,#' ## #' '# #' #' '# + ## ## ####### ## ,######, #####, # # + '#, ,#' ## ## '#, ,#' ,# #, #, # #, ,# + '#######' ## ## '#######' #' '# '####' # '####' + + + + ######################################################### + # -***- # + # Department of theory and spectroscopy # + # # + # Frank Neese # + # # + # Directorship, Architecture, Infrastructure # + # SHARK, DRIVERS # + # Core code/Algorithms in most modules # + # # + # Max Planck Institute fuer Kohlenforschung # + # Kaiser Wilhelm Platz 1 # + # D-45470 Muelheim/Ruhr # + # Germany # + # # + # All rights reserved # + # -***- # + ######################################################### + + + Program Version 6.0.0 - RELEASE - + + + With contributions from (in alphabetic order): + Daniel Aravena : Magnetic Suceptibility + Michael Atanasov : Ab Initio Ligand Field Theory (pilot matlab implementation) + Alexander A. Auer : GIAO ZORA, VPT2 properties, NMR spectrum + Ute Becker : All parallelization in ORCA, NUMFREQ, NUMCALC + Giovanni Bistoni : ED, misc. LED, open-shell LED, HFLD + Martin Brehm : Molecular dynamics + Dmytro Bykov : pre 5.0 version of the SCF Hessian + Marcos Casanova-Páez : Triplet and SCS-CIS(D). UHF-(DLPNO)-IP/EA/STEOM-CCSD. UHF-CVS-IP/STEOM-CCSD + Vijay G. Chilkuri : MRCI spin determinant printing, contributions to CSF-ICE + Pauline Colinet : FMM embedding + Dipayan Datta : RHF DLPNO-CCSD density + Achintya Kumar Dutta : EOM-CC, STEOM-CC + Nicolas Foglia : Exact transition moments, OPA infrastructure, MCD improvements + Dmitry Ganyushin : Spin-Orbit,Spin-Spin,Magnetic field MRCI + Miquel Garcia : C-PCM and meta-GGA Hessian, CCSD/C-PCM, Gaussian charge scheme + Tiago L. C. Gouveia : GS-ROHF, GS-ROCIS + Yang Guo : DLPNO-NEVPT2, F12-NEVPT2, CIM, IAO-localization + Andreas Hansen : Spin unrestricted coupled pair/coupled cluster methods + Ingolf Harden : AUTO-CI MPn and infrastructure + Benjamin Helmich-Paris : MC-RPA, TRAH-(SCF,CASSCF), AVAS, COSX integrals, SCF dyn. polar. + Lee Huntington : MR-EOM, pCC + Robert Izsak : Overlap fitted RIJCOSX, COSX-SCS-MP3, EOM + Riya Kayal : Wick's Theorem for AUTO-CI, AUTO-CI UHF-CCSDT + Emily Kempfer : AUTO-CI, RHF CISDT and CCSDT + Christian Kollmar : KDIIS, OOCD, Brueckner-CCSD(T), CCSD density, CASPT2, CASPT2-K, improved NEVPT2 + Axel Koslowski : Symmetry handling + Simone Kossmann : Meta GGA functionals, TD-DFT gradient, OOMP2, (MP2 Hessian; deprecated post 5.0) + Lucas Lang : DCDCAS + Marvin Lechner : AUTO-CI (C++ implementation), FIC-MRCC + Spencer Leger : CASSCF response + Dagmar Lenk : GEPOL surface, SMD, ORCA-2-JSON + Dimitrios Liakos : Extrapolation schemes; Compound Job, initial MDCI parallelization + Dimitrios Manganas : Further ROCIS development; embedding schemes. LFT, Crystal Embedding + Dimitrios Pantazis : SARC Basis sets + Anastasios Papadopoulos: AUTO-CI, single reference methods and gradients + Taras Petrenko : pre 6.0 DFT Hessian and TD-DFT gradient, (ASA, deprecated), ECA, 1-Electron XAS/XES, NRVS + Peter Pinski : DLPNO-MP2, DLPNO-MP2 Gradient + Christoph Reimann : Effective Core Potentials + Marius Retegan : Local ZFS, SOC + Christoph Riplinger : Optimizer, TS searches, QM/MM, DLPNO-CCSD(T), (RO)-DLPNO pert. Triples + Michael Roemelt : Original ROCIS implementation + Masaaki Saitow : Open-shell DLPNO-CCSD energy and density + Barbara Sandhoefer : DKH picture change effects + Kantharuban Sivalingam : CASSCF convergence/infrastructure, NEVPT2 and variants, FIC-MRCI + Bernardo de Souza : ESD, SOC TD-DFT + Georgi Stoychev : AutoAux, RI-MP2 NMR, DLPNO-MP2 response, X2C + Van Anh Tran : RI-MP2 g-tensors + Willem Van den Heuvel : Paramagnetic NMR + Zikuan Wang : NOTCH, Electric field optimization + Frank Wennmohs : Technical directorship and infrastructure + Hang Xu : AUTO-CI-Response properties + + + We gratefully acknowledge several colleagues who have allowed us to + interface, adapt or use parts of their codes: + Stefan Grimme, W. Hujo, H. Kruse, P. Pracht, : VdW corrections, initial TS optimization, + C. Bannwarth, S. Ehlert, DFT functionals, gCP, sTDA/sTD-DF + L. Wittmann, M. Mueller + Ed Valeev, F. Pavosevic, A. Kumar : LibInt (2-el integral package), F12 methods + Garnet Chan, S. Sharma, J. Yang, R. Olivares : DMRG + Ulf Ekstrom : XCFun DFT Library + Mihaly Kallay : mrcc (arbitrary order and MRCC methods) + Frank Weinhold : gennbo (NPA and NBO analysis) + Simon Mueller : openCOSMO-RS + Christopher J. Cramer and Donald G. Truhlar : smd solvation model + Lars Goerigk : TD-DFT with DH, B97 family of functionals + V. Asgeirsson, H. Jonsson : NEB implementation + FAccTs GmbH : IRC, NEB, NEB-TS, DLPNO-Multilevel, CI-OPT + MM, QMMM, 2- and 3-layer-ONIOM, Crystal-QMMM, + LR-CPCM, SF, NACMEs, symmetry and pop. for TD-DFT, + nearIR, NL-DFT gradient (VV10), updates on ESD, + ML-optimized integration grids, MBIS, APM, + GOAT, DOCKER, SOLVATOR, interface openCOSMO-RS + S Lehtola, MJT Oliveira, MAL Marques : LibXC Library + Liviu Ungur et al : ANISO software + + + Your calculation uses the libint2 library for the computation of 2-el integrals + For citations please refer to: http://libint.valeyev.net + + Your ORCA version has been built with support for libXC version: 6.2.2 + For citations please refer to: https://libxc.gitlab.io + + This ORCA versions uses: + CBLAS interface : Fast vector & matrix operations + LAPACKE interface : Fast linear algebra routines + SCALAPACK package : Parallel linear algebra routines + Shared memory : Shared parallel matrices + BLAS/LAPACK : OpenBLAS 0.3.27 USE64BITINT DYNAMIC_ARCH NO_AFFINITY Cooperlake SINGLE_THREADED + Core in use : Cooperlake + Copyright (c) 2011-2014, The OpenBLAS Project + + +NOTE: MaxCore=1792 MB was set to SCF,MP2,MDCI,CIPSI,MRCI and CIS + => If you want to overwrite this, your respective input block should be placed after the MaxCore statement + + +*************************************** +The coordinates will be read from file: /home/kaplan.kfir/Code/runs/test_orca_adapter/reactant.xyz +*************************************** + + +Your calculation utilizes a Nudged-Elastic-Band implementation + by V.Asgeirsson, C. Riplinger & H. Jonsson +Please cite in your paper: + V. Asgeirsson et al., in prep. (2019) + + +Warning: RI is on but no J-basis has been assigned. Assigning Def2/J (nothing to worry about!) +================================================================================ + +----- Orbital basis set information ----- +Your calculation utilizes the basis: STO-3G + H-Ne : W. J. Hehre, R. F. Stewart and J. A. Pople, J. Chem. Phys. 2657 (1969). + Na-Ar : W. J. Hehre, R. Ditchfield, R. F. Stewart and J. A. Pople, J. Chem. Phys. 2769 (1970). + K,Ca,Ga-Kr : W. J. Pietro, B. A. Levy, W. J. Hehre and R. F. Stewart, J. Am. Chem. Soc. 19, 2225 (1980). + Sc-Zn,Y-Cd : W. J. Pietro and W. J. Hehre, J. Comp. Chem. 4, 241 (1983). + +----- AuxJ basis set information ----- +Your calculation utilizes the auxiliary basis: def2/J + F. Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006). + +================================================================================ + WARNINGS + Please study these warnings very carefully! +================================================================================ + + +WARNING: Geometry Optimization + ===> : Switching off AutoStart + For restart on a previous wavefunction, please use MOREAD + +================================================================================ + INPUT FILE +================================================================================ +NAME = input.in +| 1> +| 2> !uHF b3lyp sto-3g NEB-TS +| 3> %maxcore 1792 +| 4> %pal nprocs 8 end +| 5> +| 6> %neb +| 7> Interpolation IDPP +| 8> NImages 15 +| 9> PrintLevel 3 +| 10> PreOpt true +| 11> NEB_END_XYZFILE "/home/kaplan.kfir/Code/runs/test_orca_adapter/product.xyz" +| 12> END +| 13> +| 14> * XYZFILE 0 2 /home/kaplan.kfir/Code/runs/test_orca_adapter/reactant.xyz +| 15> +| 16> ****END OF INPUT**** +================================================================================ + + +-------------------------------------------------------------------------------- + Nudged Elastic Band Calculation +-------------------------------------------------------------------------------- + +Number of images (incl. end points) .... 17 +Number of intermediate images .... 15 +Number of optimized images .... 15 +Optimization of end points before NEB .... YES +Use existing gbw files for MO input .... NO +Number of atoms .... 10 +Number of (active) degrees of freedom .... 30 +Constrained atoms .... None + + +Before the actual NEB run reactant and product are preoptimized. + +--------------------------------------------------------------- + REACTANT OPTIMIZATION +--------------------------------------------------------------- + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 50 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 10 +The number of degrees of freedom .... 24 + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(C 1,C 0) 1.4874 0.436819 + 2. B(C 2,C 1) 1.4874 0.436819 + 3. B(H 3,C 0) 1.0936 0.355309 + 4. B(H 4,C 0) 1.0939 0.355039 + 5. B(H 5,C 0) 1.0940 0.354789 + 6. B(H 6,C 1) 1.0847 0.367157 + 7. B(H 7,C 2) 1.0936 0.355309 + 8. B(H 8,C 2) 1.0940 0.354789 + 9. B(H 9,C 2) 1.0939 0.355039 + 10. A(H 3,C 0,H 4) 109.0040 0.289585 + 11. A(C 1,C 0,H 3) 110.4180 0.332060 + 12. A(C 1,C 0,H 5) 110.0120 0.331980 + 13. A(H 4,C 0,H 5) 107.9848 0.289518 + 14. A(C 1,C 0,H 4) 111.0052 0.332018 + 15. A(H 3,C 0,H 5) 108.3405 0.289553 + 16. A(C 0,C 1,C 2) 119.7740 0.383479 + 17. A(C 2,C 1,H 6) 119.2330 0.333872 + 18. A(C 0,C 1,H 6) 119.2330 0.333872 + 19. A(H 7,C 2,H 9) 109.0040 0.289585 + 20. A(C 1,C 2,H 9) 111.0052 0.332018 + 21. A(H 7,C 2,H 8) 108.3405 0.289553 + 22. A(C 1,C 2,H 8) 110.0119 0.331980 + 23. A(H 8,C 2,H 9) 107.9849 0.289518 + 24. A(C 1,C 2,H 7) 110.4180 0.332060 + 25. D(C 2,C 1,C 0,H 4) -46.5024 0.014083 + 26. D(H 6,C 1,C 0,H 3) -90.2750 0.014083 + 27. D(C 2,C 1,C 0,H 3) 74.5039 0.014083 + 28. D(H 6,C 1,C 0,H 4) 148.7186 0.014083 + 29. D(C 2,C 1,C 0,H 5) -165.9641 0.014083 + 30. D(H 7,C 2,C 1,H 6) 90.2750 0.014083 + 31. D(H 7,C 2,C 1,C 0) -74.5039 0.014083 + 32. D(H 9,C 2,C 1,C 0) 46.5024 0.014083 + 33. D(H 8,C 2,C 1,H 6) -29.2570 0.014083 + 34. D(H 8,C 2,C 1,C 0) 165.9640 0.014083 + ----------------------------------------------------------------- + +Number of atoms .... 10 +Number of degrees of freedom .... 34 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.293239 -0.026132 0.180614 + C 0.047605 0.461389 -0.239975 + C 1.250435 -0.376919 0.010777 + H -1.404815 0.052776 1.265688 + H -1.443190 -1.067676 -0.118073 + H -2.075450 0.576386 -0.290610 + H 0.175051 1.508318 -0.493563 + H 1.519732 -0.350535 1.070420 + H 2.097649 0.000892 -0.569242 + H 1.073856 -1.414791 -0.286131 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.443868 -0.049382 0.341311 + 1 C 6.0000 0 12.011 0.089961 0.871899 -0.453488 + 2 C 6.0000 0 12.011 2.362980 -0.712273 0.020365 + 3 H 1.0000 0 1.008 -2.654716 0.099732 2.391804 + 4 H 1.0000 0 1.008 -2.727234 -2.017615 -0.223126 + 5 H 1.0000 0 1.008 -3.922032 1.089211 -0.549173 + 6 H 1.0000 0 1.008 0.330798 2.850309 -0.932699 + 7 H 1.0000 0 1.008 2.871876 -0.662415 2.022801 + 8 H 1.0000 0 1.008 3.963982 0.001685 -1.075711 + 9 H 1.0000 0 1.008 2.029294 -2.673568 -0.540710 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.487425914027 0.00000000 0.00000000 + C 2 1 0 1.487425980527 119.77399045 0.00000000 + H 1 2 3 1.093645997827 110.41802604 74.50386961 + H 1 2 3 1.093852738124 111.00517693 313.49755566 + H 1 2 3 1.094044400362 110.01195059 194.03594548 + H 2 1 3 1.084716628382 119.23299408 195.22108514 + H 3 2 1 1.093646008193 110.41801850 285.49610873 + H 3 2 1 1.094044350795 110.01194450 165.96404977 + H 3 2 1 1.093852602978 111.00522169 46.50237252 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.810827622008 0.00000000 0.00000000 + C 2 1 0 2.810827747675 119.77399045 0.00000000 + H 1 2 3 2.066691423352 110.41802604 74.50386961 + H 1 2 3 2.067082105895 111.00517693 313.49755566 + H 1 2 3 2.067444295035 110.01195059 194.03594548 + H 2 1 3 2.049817360552 119.23299408 195.22108514 + H 3 2 1 2.066691442941 110.41801850 285.49610873 + H 3 2 1 2.067444201366 110.01194450 165.96404977 + H 3 2 1 2.067081850506 111.00522169 46.50237252 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 6s3p contracted to 2s1p pattern {33/3} + Group 2 Type H : 3s contracted to 1s pattern {3} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} + Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1112 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 75.729286363778 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.088e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40926 +Total number of batches ... 643 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5309 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 531 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10983 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24060 +Total number of batches ... 192 +Average number of points per batch ... 125 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input_reactant + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 75.7292863638 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 50 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +------------------------------ +INITIAL GUESS: MODEL POTENTIAL +------------------------------ +Loading Hartree-Fock densities ... done +Calculating cut-offs ... done +Initializing the effective Hamiltonian ... done +Setting up the integral package (SHARK) ... done +Starting the Coulomb interaction ... done ( 0.0 sec) +Making the grid ... done ( 0.0 sec) +Mapping shells ... done +Starting the XC term evaluation ... done ( 0.0 sec) + promolecular density results + # of electrons = 24.998908262 + EX = -17.464352202 + EC = -0.773562246 + EX+EC = -18.237914448 +Transforming the Hamiltonian ... done ( 0.0 sec) +Diagonalizing the Hamiltonian ... done ( 0.0 sec) +Back transforming the eigenvectors ... done ( 0.0 sec) +Now organizing SCF variables ... done + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.5 sec +Maximum memory used throughout the entire GUESS-calculation: 6.0 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Warning: Unable to find asked property in file 'input_reactant.property.txt' + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.9173796614736744 0.00e+00 5.94e-03 2.58e-02 4.60e-02 0.700 0.1 + 2 -116.9362188686311441 -1.88e-02 4.49e-03 2.01e-02 2.80e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -116.9458707541682116 -9.65e-03 1.82e-03 1.03e-02 1.43e-02 0.700 0.1 + 4 -116.9514457988135092 -5.58e-03 3.39e-03 2.38e-02 9.02e-03 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -116.9631051776286910 -1.17e-02 5.03e-04 4.80e-03 1.98e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -116.9631506662943110 -4.55e-05 2.59e-04 2.27e-03 8.86e-04 0.1 + 7 -116.9631595868929281 -8.92e-06 1.75e-04 1.44e-03 4.39e-04 0.1 + 8 -116.9631613538353889 -1.77e-06 3.65e-05 2.56e-04 1.33e-04 0.1 + 9 -116.9631615422277804 -1.88e-07 6.39e-06 3.20e-05 2.17e-05 0.1 + 10 -116.9631615463396344 -4.11e-09 2.50e-06 1.43e-05 8.66e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.097 sec) +Old exchange energy : -3.623635999 Eh +New exchange energy : -3.623688237 Eh +Exchange energy change after final integration : -0.000052239 Eh +Total energy after final integration : -116.963213785 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96321378498317 Eh -3182.73085 eV + +Components: +Nuclear Repulsion : 75.72928636377763 Eh 2060.69865 eV +Electronic Energy : -192.69244791011727 Eh -5243.42808 eV +One Electron Energy: -306.42041920702923 Eh -8338.12351 eV +Two Electron Energy: 113.72797129691196 Eh 3094.69543 eV + +Virial components: +Potential Energy : -232.28864985013931 Eh -6320.89551 eV +Kinetic Energy : 115.32543606515614 Eh 3138.16466 eV +Virial Ratio : 2.01420135726954 + +DFT components: +N(Alpha) : 13.000000124403 electrons +N(Beta) : 12.000000759208 electrons +N(Total) : 25.000000883611 electrons +E(X) : -14.296236581913 Eh +E(C) : -0.919052606015 Eh +E(XC) : -15.215289187928 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.1119e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4330e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.4988e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9829e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.6610e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.5466e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754059 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004059 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -9.999995 -272.1137 + 1 1.0000 -9.999977 -272.1132 + 2 1.0000 -9.968047 -271.2443 + 3 1.0000 -0.738941 -20.1076 + 4 1.0000 -0.650698 -17.7064 + 5 1.0000 -0.528452 -14.3799 + 6 1.0000 -0.410848 -11.1797 + 7 1.0000 -0.396535 -10.7903 + 8 1.0000 -0.366422 -9.9708 + 9 1.0000 -0.354224 -9.6389 + 10 1.0000 -0.304459 -8.2848 + 11 1.0000 -0.302753 -8.2383 + 12 1.0000 -0.114120 -3.1054 + 13 0.0000 0.389095 10.5878 + 14 0.0000 0.420543 11.4436 + 15 0.0000 0.438640 11.9360 + 16 0.0000 0.461479 12.5575 + 17 0.0000 0.482824 13.1383 + 18 0.0000 0.487322 13.2607 + 19 0.0000 0.499610 13.5951 + 20 0.0000 0.563124 15.3234 + 21 0.0000 0.595825 16.2132 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.001113 -272.1441 + 1 1.0000 -10.001089 -272.1435 + 2 1.0000 -9.952786 -270.8291 + 3 1.0000 -0.720045 -19.5934 + 4 1.0000 -0.648970 -17.6594 + 5 1.0000 -0.504222 -13.7206 + 6 1.0000 -0.405226 -11.0268 + 7 1.0000 -0.380254 -10.3472 + 8 1.0000 -0.361507 -9.8371 + 9 1.0000 -0.349382 -9.5072 + 10 1.0000 -0.298810 -8.1310 + 11 1.0000 -0.297046 -8.0830 + 12 0.0000 0.082932 2.2567 + 13 0.0000 0.393471 10.7069 + 14 0.0000 0.442791 12.0490 + 15 0.0000 0.449116 12.2211 + 16 0.0000 0.466907 12.7052 + 17 0.0000 0.491248 13.3675 + 18 0.0000 0.501948 13.6587 + 19 0.0000 0.502861 13.6835 + 20 0.0000 0.576770 15.6947 + 21 0.0000 0.609808 16.5937 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 C : -0.239608 -0.074134 + 1 C : -0.049532 1.036232 + 2 C : -0.239615 -0.074137 + 3 H : 0.078632 0.050706 + 4 H : 0.077836 0.019593 + 5 H : 0.077997 0.008565 + 6 H : 0.059833 -0.045695 + 7 H : 0.078644 0.050709 + 8 H : 0.077977 0.008565 + 9 H : 0.077835 0.019595 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 1.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 C s : 3.182393 s : 3.182393 + pz : 1.025540 p : 3.057215 + px : 1.000458 + py : 1.031217 + + 1 C s : 3.175010 s : 3.175010 + pz : 1.004738 p : 2.874522 + px : 0.907406 + py : 0.962378 + + 2 C s : 3.182395 s : 3.182395 + pz : 1.027864 p : 3.057219 + px : 1.007968 + py : 1.021388 + + 3 H s : 0.921368 s : 0.921368 + + 4 H s : 0.922164 s : 0.922164 + + 5 H s : 0.922003 s : 0.922003 + + 6 H s : 0.940167 s : 0.940167 + + 7 H s : 0.921356 s : 0.921356 + + 8 H s : 0.922023 s : 0.922023 + + 9 H s : 0.922165 s : 0.922165 + + +SPIN + 0 C s : -0.015601 s : -0.015601 + pz : -0.020336 p : -0.058532 + px : -0.028003 + py : -0.010194 + + 1 C s : 0.076193 s : 0.076193 + pz : 0.812896 p : 0.960039 + px : 0.039809 + py : 0.107333 + + 2 C s : -0.015602 s : -0.015602 + pz : -0.018605 p : -0.058535 + px : -0.023908 + py : -0.016022 + + 3 H s : 0.050706 s : 0.050706 + + 4 H s : 0.019593 s : 0.019593 + + 5 H s : 0.008565 s : 0.008565 + + 6 H s : -0.045695 s : -0.045695 + + 7 H s : 0.050709 s : 0.050709 + + 8 H s : 0.008565 s : 0.008565 + + 9 H s : 0.019595 s : 0.019595 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 C : -0.132228 -0.054620 + 1 C : -0.027021 0.997045 + 2 C : -0.132233 -0.054623 + 3 H : 0.044616 0.046842 + 4 H : 0.043810 0.017999 + 5 H : 0.043901 0.007681 + 6 H : 0.026837 -0.032851 + 7 H : 0.044624 0.046845 + 8 H : 0.043886 0.007681 + 9 H : 0.043809 0.018001 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 C s : 2.999206 s : 2.999206 + pz : 1.045466 p : 3.133023 + px : 1.034522 + py : 1.053035 + + 1 C s : 3.061451 s : 3.061451 + pz : 1.014247 p : 2.965570 + px : 0.958363 + py : 0.992960 + + 2 C s : 2.999207 s : 2.999207 + pz : 1.046853 p : 3.133026 + px : 1.039383 + py : 1.046790 + + 3 H s : 0.955384 s : 0.955384 + + 4 H s : 0.956190 s : 0.956190 + + 5 H s : 0.956099 s : 0.956099 + + 6 H s : 0.973163 s : 0.973163 + + 7 H s : 0.955376 s : 0.955376 + + 8 H s : 0.956114 s : 0.956114 + + 9 H s : 0.956191 s : 0.956191 + + +SPIN + 0 C s : -0.009124 s : -0.009124 + pz : -0.015380 p : -0.045496 + px : -0.022095 + py : -0.008020 + + 1 C s : 0.053536 s : 0.053536 + pz : 0.809360 p : 0.943509 + px : 0.033621 + py : 0.100529 + + 2 C s : -0.009125 s : -0.009125 + pz : -0.014056 p : -0.045498 + px : -0.018829 + py : -0.012613 + + 3 H s : 0.046842 s : 0.046842 + + 4 H s : 0.017999 s : 0.017999 + + 5 H s : 0.007681 s : 0.007681 + + 6 H s : -0.032851 s : -0.032851 + + 7 H s : 0.046845 s : 0.046845 + + 8 H s : 0.007681 s : 0.007681 + + 9 H s : 0.018001 s : 0.018001 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 C 6.2396 6.0000 -0.2396 3.9634 3.9612 0.0022 + 1 C 6.0495 6.0000 -0.0495 3.9542 3.1270 0.8272 + 2 C 6.2396 6.0000 -0.2396 3.9634 3.9612 0.0022 + 3 H 0.9214 1.0000 0.0786 0.9938 0.9912 0.0026 + 4 H 0.9222 1.0000 0.0778 0.9939 0.9936 0.0004 + 5 H 0.9220 1.0000 0.0780 0.9939 0.9938 0.0001 + 6 H 0.9402 1.0000 0.0598 0.9964 0.9943 0.0021 + 7 H 0.9214 1.0000 0.0786 0.9938 0.9912 0.0026 + 8 H 0.9220 1.0000 0.0780 0.9939 0.9938 0.0001 + 9 H 0.9222 1.0000 0.0778 0.9939 0.9936 0.0004 + + Mayer bond orders larger than 0.100000 +B( 0-C , 1-C ) : 1.0361 B( 0-C , 3-H ) : 0.9563 B( 0-C , 4-H ) : 0.9698 +B( 0-C , 5-H ) : 0.9758 B( 1-C , 2-C ) : 1.0361 B( 1-C , 6-H ) : 0.9648 +B( 2-C , 7-H ) : 0.9563 B( 2-C , 8-H ) : 0.9758 B( 2-C , 9-H ) : 0.9698 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.354 sec +Sum of individual times .... 1.329 sec ( 98.1%) + +SCF preparation .... 0.241 sec ( 17.8%) +Fock matrix formation .... 0.961 sec ( 71.0%) + Startup .... 0.011 sec ( 1.1% of F) + Split-RI-J .... 0.065 sec ( 6.8% of F) + Chain of spheres X .... 0.565 sec ( 58.8% of F) + XC integration .... 0.283 sec ( 29.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.079 sec ( 27.9% of XC) + Density eval. .... 0.024 sec ( 8.4% of XC) + XC-Functional eval. .... 0.071 sec ( 25.3% of XC) + XC-Potential eval. .... 0.021 sec ( 7.4% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.016 sec ( 1.1%) +Total Energy calculation .... 0.016 sec ( 1.2%) +Population analysis .... 0.010 sec ( 0.8%) +Orbital Transformation .... 0.012 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.045 sec ( 3.4%) +SOSCF solution .... 0.028 sec ( 2.0%) +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.5 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.963213784983 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.013040425 -0.002739956 0.004720374 + 2 C : -0.000220062 -0.006587946 0.010306227 + 3 C : -0.012556116 0.000804187 0.006432084 + 4 H : 0.005383982 0.002390807 -0.010827809 + 5 H : 0.001469056 0.007618425 -0.001480043 + 6 H : 0.006717429 -0.002466368 -0.000171731 + 7 H : -0.001298818 -0.010169735 0.001753962 + 8 H : -0.005912597 0.003943683 -0.010072453 + 9 H : -0.007090968 -0.000563155 0.000754097 + 10 H : 0.000467669 0.007770059 -0.001414709 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000370618 -0.0000346225 0.0001002978 + +Norm of the Cartesian gradient ... 0.0344770702 +RMS gradient ... 0.0062946230 +MAX gradient ... 0.0130404247 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.642 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.114 sec ( 17.8%) +COSX gradient .... 0.403 sec ( 62.9%) +XC gradient .... 0.119 sec ( 18.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.963213785 Eh +Current gradient norm .... 0.034477070 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.992443634 +Lowest eigenvalues of augmented Hessian: + -0.005807161 0.014083133 0.014083852 0.016593830 0.135071509 +Length of the computed step .... 0.123635634 +The final length of the internal step .... 0.123635634 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0212033362 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0439459732 RMS(Int)= 0.0211980511 +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0082729940 0.0001000000 NO + MAX gradient 0.0277597671 0.0003000000 NO + RMS step 0.0212033362 0.0020000000 NO + MAX step 0.0627160272 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0332 Max(Angles) 1.32 + Max(Dihed) 1.02 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.4874 -0.027760 0.0332 1.5206 + 2. B(C 2,C 1) 1.4874 -0.027750 0.0332 1.5206 + 3. B(H 3,C 0) 1.0936 -0.011118 0.0163 1.1099 + 4. B(H 4,C 0) 1.0939 -0.007054 0.0103 1.1042 + 5. B(H 5,C 0) 1.0940 -0.006086 0.0089 1.1030 + 6. B(H 6,C 1) 1.0847 -0.010378 0.0147 1.0994 + 7. B(H 7,C 2) 1.0936 -0.011121 0.0163 1.1099 + 8. B(H 8,C 2) 1.0940 -0.006086 0.0089 1.1030 + 9. B(H 9,C 2) 1.0939 -0.007061 0.0104 1.1042 + 10. A(H 3,C 0,H 4) 109.00 0.005165 -1.29 107.72 + 11. A(C 1,C 0,H 3) 110.42 -0.005665 0.90 111.32 + 12. A(C 1,C 0,H 5) 110.01 -0.004228 0.91 110.92 + 13. A(H 4,C 0,H 5) 107.98 0.001175 0.03 108.02 + 14. A(C 1,C 0,H 4) 111.01 -0.000460 0.06 111.07 + 15. A(H 3,C 0,H 5) 108.34 0.004366 -0.68 107.66 + 16. A(C 0,C 1,C 2) 119.77 -0.005619 0.82 120.60 + 17. A(C 2,C 1,H 6) 119.23 0.002746 -0.48 118.75 + 18. A(C 0,C 1,H 6) 119.23 0.002907 -0.48 118.75 + 19. A(H 7,C 2,H 9) 109.00 0.005619 -1.32 107.69 + 20. A(C 1,C 2,H 9) 111.01 -0.000471 0.07 111.07 + 21. A(H 7,C 2,H 8) 108.34 0.004380 -0.69 107.65 + 22. A(C 1,C 2,H 8) 110.01 -0.004454 0.92 110.93 + 23. A(H 8,C 2,H 9) 107.98 0.000684 0.08 108.06 + 24. A(C 1,C 2,H 7) 110.42 -0.005414 0.88 111.30 + 25. D(C 2,C 1,C 0,H 4) -46.50 -0.001080 0.37 -46.14 + 26. D(H 6,C 1,C 0,H 3) -90.28 0.000750 0.04 -90.23 + 27. D(C 2,C 1,C 0,H 3) 74.50 0.001320 -0.61 73.89 + 28. D(H 6,C 1,C 0,H 4) 148.72 -0.001651 1.02 149.74 + 29. D(C 2,C 1,C 0,H 5) -165.96 0.000482 -0.30 -166.27 + 30. D(H 7,C 2,C 1,H 6) 90.28 -0.000552 -0.19 90.09 + 31. D(H 7,C 2,C 1,C 0) -74.50 -0.001147 0.46 -74.04 + 32. D(H 9,C 2,C 1,C 0) 46.50 0.001988 -0.56 45.94 + 33. D(H 8,C 2,C 1,H 6) -29.26 0.000254 -0.48 -29.73 + 34. D(H 8,C 2,C 1,C 0) 165.96 -0.000340 0.17 166.14 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.012 %) +Internal coordinates : 0.000 s ( 3.234 %) +B/P matrices and projection : 0.000 s (20.945 %) +Hessian update/contruction : 0.000 s (11.294 %) +Making the step : 0.000 s (15.246 %) +Converting the step to Cartesian: 0.000 s ( 3.696 %) +Storing new data : 0.000 s ( 2.310 %) +Checking convergence : 0.000 s ( 0.103 %) +Final printing : 0.001 s (30.185 %) +Total time : 0.002 s + +Time for energy+gradient : 6.388 s +Time for complete geometry iter : 7.203 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.326927 -0.019161 0.178512 + C 0.047982 0.468904 -0.250071 + C 1.284302 -0.379053 0.004318 + H -1.454734 0.050034 1.278894 + H -1.482419 -1.072987 -0.112224 + H -2.122601 0.584679 -0.289287 + H 0.177837 1.531778 -0.499491 + H 1.569581 -0.364285 1.076872 + H 2.144721 -0.005057 -0.575649 + H 1.109892 -1.431144 -0.281969 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.507529 -0.036209 0.337338 + 1 C 6.0000 0 12.011 0.090673 0.886100 -0.472566 + 2 C 6.0000 0 12.011 2.426979 -0.716307 0.008161 + 3 H 1.0000 0 1.008 -2.749049 0.094551 2.416759 + 4 H 1.0000 0 1.008 -2.801365 -2.027651 -0.212072 + 5 H 1.0000 0 1.008 -4.011135 1.104884 -0.546674 + 6 H 1.0000 0 1.008 0.336062 2.894640 -0.943902 + 7 H 1.0000 0 1.008 2.966077 -0.688399 2.034993 + 8 H 1.0000 0 1.008 4.052936 -0.009555 -1.087818 + 9 H 1.0000 0 1.008 2.097391 -2.704470 -0.532845 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.520613806807 0.00000000 0.00000000 + C 2 1 0 1.520602801530 120.59746167 0.00000000 + H 1 2 3 1.109938688439 111.31692706 73.88995613 + H 1 2 3 1.104197970330 111.06568831 313.86572937 + H 1 2 3 1.102975960112 110.91663413 193.73516745 + H 2 1 3 1.099441953038 118.75221851 195.87328612 + H 3 2 1 1.109942554263 111.29746204 285.96355728 + H 3 2 1 1.102976294693 110.92799727 166.13735193 + H 3 2 1 1.104207689261 111.07131463 45.94006753 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.873543650324 0.00000000 0.00000000 + C 2 1 0 2.873522853364 120.59746167 0.00000000 + H 1 2 3 2.097480146594 111.31692706 73.88995613 + H 1 2 3 2.086631761555 111.06568831 313.86572937 + H 1 2 3 2.084322496911 110.91663413 193.73516745 + H 2 1 3 2.077644191386 118.75221851 195.87328612 + H 3 2 1 2.097487451942 111.29746204 285.96355728 + H 3 2 1 2.084323129178 110.92799727 166.13735193 + H 3 2 1 2.086650127673 111.07131463 45.94006753 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.293943490105 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.208e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40953 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10997 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24081 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9658798211887785 0.00e+00 1.04e-03 8.29e-03 1.22e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9661035379313461 -2.24e-04 4.75e-04 3.27e-03 1.19e-03 0.1 + 3 -116.9661243202077543 -2.08e-05 1.70e-04 1.13e-03 5.80e-04 0.1 + 4 -116.9661269045597720 -2.58e-06 5.33e-05 4.94e-04 1.98e-04 0.1 + 5 -116.9661273343721604 -4.30e-07 8.94e-06 5.29e-05 2.95e-05 0.1 + 6 -116.9661273407864570 -6.41e-09 3.30e-06 1.97e-05 1.63e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.614237476 Eh +New exchange energy : -3.614285159 Eh +Exchange energy change after final integration : -0.000047683 Eh +Total energy after final integration : -116.966175024 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96617502409320 Eh -3182.81143 eV + +Components: +Nuclear Repulsion : 74.29394349010515 Eh 2021.64098 eV +Electronic Energy : -191.26007083089161 Eh -5204.45112 eV +One Electron Energy: -303.66929262763369 Eh -8263.26155 eV +Two Electron Energy: 112.40922179674209 Eh 3058.81043 eV + +Virial components: +Potential Energy : -232.15436361305569 Eh -6317.24140 eV +Kinetic Energy : 115.18818858896248 Eh 3134.42996 eV +Virial Ratio : 2.01543549262221 + +DFT components: +N(Alpha) : 12.999998623844 electrons +N(Beta) : 11.999998897936 electrons +N(Total) : 24.999997521779 electrons +E(X) : -14.264558231040 Eh +E(C) : -0.915726044705 Eh +E(XC) : -15.180284275746 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4143e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9715e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.3046e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2724e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.6274e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2966e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754348 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004348 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.7 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966175024093 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.001787522 -0.001716212 -0.000016276 + 2 C : 0.000185947 0.000143655 0.002422551 + 3 C : -0.002119182 -0.001136814 0.000112377 + 4 H : 0.000876516 0.001120178 0.001603423 + 5 H : -0.000509622 -0.000320589 -0.001439417 + 6 H : -0.000505143 0.000266305 -0.000994347 + 7 H : 0.000011209 0.000661814 -0.000936566 + 8 H : -0.000352290 0.001260678 0.001668440 + 9 H : 0.000440417 0.000178408 -0.001012770 + 10 H : 0.000184626 -0.000457423 -0.001407414 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000307882 -0.0000280687 0.0000857418 + +Norm of the Cartesian gradient ... 0.0059575208 +RMS gradient ... 0.0010876895 +MAX gradient ... 0.0024225507 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.660 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 17.7%) +COSX gradient .... 0.415 sec ( 62.9%) +XC gradient .... 0.123 sec ( 18.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966175024 Eh +Current gradient norm .... 0.005957521 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998885572 +Lowest eigenvalues of augmented Hessian: + -0.000135620 0.014080935 0.014083138 0.016565449 0.133653200 +Length of the computed step .... 0.047250265 +The final length of the internal step .... 0.047250265 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0081033536 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0065958083 RMS(Int)= 0.0080921663 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000067961 +Previously predicted energy change .... -0.002947964 +Actually observed energy change .... -0.002961239 +Ratio of predicted to observed change .... 1.004503076 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0029612391 0.0000050000 NO + RMS gradient 0.0009477125 0.0001000000 NO + MAX gradient 0.0016786297 0.0003000000 NO + RMS step 0.0081033536 0.0020000000 NO + MAX step 0.0245054263 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0026 Max(Angles) 0.46 + Max(Dihed) 1.40 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5206 -0.001524 0.0026 1.5232 + 2. B(C 2,C 1) 1.5206 -0.001519 0.0026 1.5232 + 3. B(H 3,C 0) 1.1099 0.001560 -0.0021 1.1078 + 4. B(H 4,C 0) 1.1042 0.000754 -0.0010 1.1032 + 5. B(H 5,C 0) 1.1030 0.000933 -0.0013 1.1017 + 6. B(H 6,C 1) 1.0994 0.000853 -0.0010 1.0985 + 7. B(H 7,C 2) 1.1099 0.001538 -0.0021 1.1079 + 8. B(H 8,C 2) 1.1030 0.000936 -0.0013 1.1017 + 9. B(H 9,C 2) 1.1042 0.000774 -0.0010 1.1032 + 10. A(H 3,C 0,H 4) 107.72 0.001436 -0.45 107.27 + 11. A(C 1,C 0,H 3) 111.32 -0.001679 0.29 111.60 + 12. A(C 1,C 0,H 5) 110.92 -0.000340 0.15 111.07 + 13. A(H 4,C 0,H 5) 108.01 -0.000414 0.18 108.20 + 14. A(C 1,C 0,H 4) 111.07 0.000296 -0.07 111.00 + 15. A(H 3,C 0,H 5) 107.65 0.000795 -0.12 107.54 + 16. A(C 0,C 1,C 2) 120.60 -0.001393 0.15 120.74 + 17. A(C 2,C 1,H 6) 118.75 0.000729 -0.25 118.51 + 18. A(C 0,C 1,H 6) 118.75 0.000768 -0.24 118.51 + 19. A(H 7,C 2,H 9) 107.69 0.001610 -0.46 107.23 + 20. A(C 1,C 2,H 9) 111.07 0.000273 -0.06 111.01 + 21. A(H 7,C 2,H 8) 107.64 0.000846 -0.14 107.51 + 22. A(C 1,C 2,H 8) 110.93 -0.000435 0.15 111.08 + 23. A(H 8,C 2,H 9) 108.06 -0.000642 0.21 108.27 + 24. A(C 1,C 2,H 7) 111.30 -0.001558 0.27 111.57 + 25. D(C 2,C 1,C 0,H 4) -46.13 -0.000316 -0.08 -46.22 + 26. D(H 6,C 1,C 0,H 3) -90.24 0.000026 0.99 -89.25 + 27. D(C 2,C 1,C 0,H 3) 73.89 0.000576 -0.50 73.39 + 28. D(H 6,C 1,C 0,H 4) 149.74 -0.000866 1.40 151.14 + 29. D(C 2,C 1,C 0,H 5) -166.26 0.000236 -0.37 -166.63 + 30. D(H 7,C 2,C 1,H 6) 90.09 0.000068 -1.07 89.02 + 31. D(H 7,C 2,C 1,C 0) -74.04 -0.000488 0.42 -73.62 + 32. D(H 9,C 2,C 1,C 0) 45.94 0.000689 -0.01 45.93 + 33. D(H 8,C 2,C 1,H 6) -29.74 0.000325 -1.17 -30.91 + 34. D(H 8,C 2,C 1,C 0) 166.14 -0.000231 0.31 166.45 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.101 %) +Internal coordinates : 0.000 s ( 0.192 %) +B/P matrices and projection : 0.000 s ( 1.520 %) +Hessian update/contruction : 0.022 s (92.324 %) +Making the step : 0.000 s ( 1.400 %) +Converting the step to Cartesian: 0.000 s ( 0.320 %) +Storing new data : 0.000 s ( 0.290 %) +Checking convergence : 0.000 s ( 0.085 %) +Final printing : 0.001 s ( 2.754 %) +Total time : 0.023 s + +Time for energy+gradient : 5.354 s +Time for complete geometry iter : 6.218 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.330041 -0.017615 0.176520 + C 0.047262 0.467180 -0.257269 + C 1.287436 -0.378338 0.001924 + H -1.458898 0.049658 1.274790 + H -1.485498 -1.072267 -0.107507 + H -2.126522 0.584910 -0.288604 + H 0.178624 1.532647 -0.489935 + H 1.573563 -0.364328 1.072132 + H 2.148441 -0.006476 -0.576121 + H 1.113266 -1.431662 -0.276026 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.513414 -0.033288 0.333575 + 1 C 6.0000 0 12.011 0.089313 0.882843 -0.486167 + 2 C 6.0000 0 12.011 2.432901 -0.714955 0.003637 + 3 H 1.0000 0 1.008 -2.756918 0.093841 2.409003 + 4 H 1.0000 0 1.008 -2.807184 -2.026291 -0.203158 + 5 H 1.0000 0 1.008 -4.018544 1.105319 -0.545383 + 6 H 1.0000 0 1.008 0.337550 2.896283 -0.925844 + 7 H 1.0000 0 1.008 2.973603 -0.688481 2.026036 + 8 H 1.0000 0 1.008 4.059965 -0.012238 -1.088711 + 9 H 1.0000 0 1.008 2.103767 -2.705449 -0.521613 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.523208766385 0.00000000 0.00000000 + C 2 1 0 1.523191581725 120.73524841 0.00000000 + H 1 2 3 1.107847247819 111.60269388 73.39005420 + H 1 2 3 1.103235375966 110.99892976 313.78469440 + H 1 2 3 1.101706808121 111.06365110 193.37032368 + H 2 1 3 1.098457660151 118.50053753 197.35944067 + H 3 2 1 1.107885104062 111.56983738 286.38136026 + H 3 2 1 1.101702440330 111.07960040 166.45078735 + H 3 2 1 1.103214716088 111.01301208 45.92423273 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.878447413256 0.00000000 0.00000000 + C 2 1 0 2.878414938955 120.73524841 0.00000000 + H 1 2 3 2.093527896597 111.60269388 73.39005420 + H 1 2 3 2.084812721829 110.99892976 313.78469440 + H 1 2 3 2.081924147225 111.06365110 193.37032368 + H 2 1 3 2.075784147393 118.50053753 197.35944067 + H 3 2 1 2.093599434527 111.56983738 286.38136026 + H 3 2 1 2.081915893297 111.07960040 166.45078735 + H 3 2 1 2.084773680318 111.01301208 45.92423273 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.239861032167 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.208e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40952 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10996 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24083 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9661776619582838 0.00e+00 3.85e-04 4.47e-03 9.10e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662072859854334 -2.96e-05 2.43e-04 2.81e-03 1.21e-03 0.1 + 3 -116.9662144818035756 -7.20e-06 7.79e-05 8.49e-04 2.74e-04 0.1 + 4 -116.9662149761773833 -4.94e-07 2.02e-05 9.38e-05 6.54e-05 0.1 + 5 -116.9662150085952135 -3.24e-08 7.52e-06 4.28e-05 3.08e-05 0.1 + 6 -116.9662150186215115 -1.00e-08 6.06e-07 3.83e-06 2.22e-06 0.1 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.614403778 Eh +New exchange energy : -3.614451354 Eh +Exchange energy change after final integration : -0.000047577 Eh +Total energy after final integration : -116.966262595 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96626259524041 Eh -3182.81382 eV + +Components: +Nuclear Repulsion : 74.23986103216720 Eh 2020.16932 eV +Electronic Energy : -191.20607605078874 Eh -5202.98184 eV +One Electron Energy: -303.55543892980535 Eh -8260.16343 eV +Two Electron Energy: 112.34936287901662 Eh 3057.18159 eV + +Virial components: +Potential Energy : -232.15588405562903 Eh -6317.28277 eV +Kinetic Energy : 115.18962146038861 Eh 3134.46895 eV +Virial Ratio : 2.01542362161041 + +DFT components: +N(Alpha) : 12.999998214094 electrons +N(Beta) : 11.999998399564 electrons +N(Total) : 24.999996613658 electrons +E(X) : -14.265014972496 Eh +E(C) : -0.915688853324 Eh +E(XC) : -15.180703825820 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0026e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.8306e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 6.0610e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.3601e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2231e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.4863e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754309 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004309 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966262595240 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000272473 -0.000763530 0.000469945 + 2 C : 0.000248462 0.001359266 0.000899952 + 3 C : 0.000159827 -0.000829369 0.000185529 + 4 H : 0.000331497 0.000267488 -0.000025675 + 5 H : -0.000257322 0.000166159 -0.000456310 + 6 H : -0.000096418 -0.000181999 -0.000130631 + 7 H : -0.000089965 -0.000283325 -0.000538568 + 8 H : -0.000267036 0.000323478 0.000008194 + 9 H : 0.000054208 -0.000123457 -0.000050477 + 10 H : 0.000189219 0.000065288 -0.000361957 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000290430 -0.0000265350 0.0000817609 + +Norm of the Cartesian gradient ... 0.0023738169 +RMS gradient ... 0.0004333977 +MAX gradient ... 0.0013592661 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.652 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.115 sec ( 17.7%) +COSX gradient .... 0.411 sec ( 63.0%) +XC gradient .... 0.120 sec ( 18.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966262595 Eh +Current gradient norm .... 0.002373817 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998457571 +Lowest eigenvalues of augmented Hessian: + -0.000042792 0.011109560 0.014083148 0.014802101 0.127592004 +Length of the computed step .... 0.055605853 +The final length of the internal step .... 0.055605853 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0095363251 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0065544111 RMS(Int)= 0.0095157514 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000021462 +Previously predicted energy change .... -0.000067961 +Actually observed energy change .... -0.000087571 +Ratio of predicted to observed change .... 1.288542634 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000875711 0.0000050000 NO + RMS gradient 0.0002716774 0.0001000000 NO + MAX gradient 0.0005591037 0.0003000000 NO + RMS step 0.0095363251 0.0020000000 NO + MAX step 0.0293700721 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.27 + Max(Dihed) 1.68 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5232 0.000386 0.0001 1.5233 + 2. B(C 2,C 1) 1.5232 0.000389 0.0001 1.5233 + 3. B(H 3,C 0) 1.1078 -0.000047 -0.0002 1.1077 + 4. B(H 4,C 0) 1.1032 -0.000008 -0.0001 1.1031 + 5. B(H 5,C 0) 1.1017 0.000026 -0.0002 1.1015 + 6. B(H 6,C 1) 1.0985 -0.000172 0.0003 1.0987 + 7. B(H 7,C 2) 1.1079 -0.000058 -0.0002 1.1077 + 8. B(H 8,C 2) 1.1017 0.000026 -0.0002 1.1015 + 9. B(H 9,C 2) 1.1032 0.000001 -0.0001 1.1031 + 10. A(H 3,C 0,H 4) 107.27 0.000413 -0.27 107.00 + 11. A(C 1,C 0,H 3) 111.60 -0.000559 0.18 111.79 + 12. A(C 1,C 0,H 5) 111.06 0.000133 0.03 111.09 + 13. A(H 4,C 0,H 5) 108.20 -0.000295 0.16 108.35 + 14. A(C 1,C 0,H 4) 111.00 0.000184 -0.07 110.93 + 15. A(H 3,C 0,H 5) 107.53 0.000136 -0.05 107.48 + 16. A(C 0,C 1,C 2) 120.74 -0.000530 0.05 120.79 + 17. A(C 2,C 1,H 6) 118.50 0.000306 -0.24 118.26 + 18. A(C 0,C 1,H 6) 118.50 0.000300 -0.23 118.27 + 19. A(H 7,C 2,H 9) 107.23 0.000441 -0.26 106.97 + 20. A(C 1,C 2,H 9) 111.01 0.000175 -0.06 110.95 + 21. A(H 7,C 2,H 8) 107.50 0.000154 -0.06 107.44 + 22. A(C 1,C 2,H 8) 111.08 0.000114 0.03 111.11 + 23. A(H 8,C 2,H 9) 108.27 -0.000345 0.16 108.43 + 24. A(C 1,C 2,H 7) 111.57 -0.000528 0.18 111.75 + 25. D(C 2,C 1,C 0,H 4) -46.22 -0.000082 -0.07 -46.29 + 26. D(H 6,C 1,C 0,H 3) -89.25 -0.000146 1.42 -87.83 + 27. D(C 2,C 1,C 0,H 3) 73.39 0.000191 -0.33 73.06 + 28. D(H 6,C 1,C 0,H 4) 151.14 -0.000420 1.68 152.83 + 29. D(C 2,C 1,C 0,H 5) -166.63 0.000079 -0.25 -166.88 + 30. D(H 7,C 2,C 1,H 6) 89.02 0.000183 -1.49 87.54 + 31. D(H 7,C 2,C 1,C 0) -73.62 -0.000154 0.27 -73.35 + 32. D(H 9,C 2,C 1,C 0) 45.92 0.000170 0.02 45.94 + 33. D(H 8,C 2,C 1,H 6) -30.91 0.000265 -1.55 -32.46 + 34. D(H 8,C 2,C 1,C 0) 166.45 -0.000071 0.20 166.65 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (16.007 %) +Internal coordinates : 0.000 s ( 2.065 %) +B/P matrices and projection : 0.000 s (16.437 %) +Hessian update/contruction : 0.000 s (15.577 %) +Making the step : 0.000 s (12.091 %) +Converting the step to Cartesian: 0.000 s ( 2.496 %) +Storing new data : 0.000 s ( 1.936 %) +Checking convergence : 0.000 s ( 0.818 %) +Final printing : 0.001 s (32.444 %) +Total time : 0.002 s + +Time for energy+gradient : 5.611 s +Time for complete geometry iter : 6.458 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.330492 -0.017128 0.174104 + C 0.046442 0.464779 -0.264533 + C 1.287651 -0.377931 -0.000424 + H -1.459577 0.051500 1.272074 + H -1.485251 -1.073505 -0.103462 + H -2.127655 0.584052 -0.291033 + H 0.179889 1.534658 -0.476099 + H 1.574862 -0.361681 1.069298 + H 2.148758 -0.008036 -0.579128 + H 1.113004 -1.433000 -0.270893 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.514265 -0.032366 0.329009 + 1 C 6.0000 0 12.011 0.087764 0.878304 -0.499894 + 2 C 6.0000 0 12.011 2.433309 -0.714186 -0.000802 + 3 H 1.0000 0 1.008 -2.758201 0.097321 2.403872 + 4 H 1.0000 0 1.008 -2.806717 -2.028630 -0.195514 + 5 H 1.0000 0 1.008 -4.020685 1.103699 -0.549973 + 6 H 1.0000 0 1.008 0.339941 2.900083 -0.899696 + 7 H 1.0000 0 1.008 2.976058 -0.683477 2.020681 + 8 H 1.0000 0 1.008 4.060565 -0.015186 -1.094394 + 9 H 1.0000 0 1.008 2.103273 -2.707978 -0.511914 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.523346345964 0.00000000 0.00000000 + C 2 1 0 1.523322745967 120.76806238 0.00000000 + H 1 2 3 1.107660274947 111.78727464 73.05800263 + H 1 2 3 1.103143589040 110.93391974 313.71429220 + H 1 2 3 1.101471210738 111.09474256 193.12285587 + H 2 1 3 1.098730969443 118.24655057 199.11139299 + H 3 2 1 1.107727858900 111.75103927 286.64772154 + H 3 2 1 1.101465278466 111.10824091 166.65102887 + H 3 2 1 1.103098619786 110.95317716 45.93985291 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.878707400982 0.00000000 0.00000000 + C 2 1 0 2.878662803450 120.76806238 0.00000000 + H 1 2 3 2.093174569073 111.78727464 73.05800263 + H 1 2 3 2.084639269677 110.93391974 313.71429220 + H 1 2 3 2.081478932694 111.09474256 193.12285587 + H 2 1 3 2.076300627104 118.24655057 199.11139299 + H 3 2 1 2.093302284236 111.75103927 286.64772154 + H 3 2 1 2.081467722324 111.10824091 166.65102887 + H 3 2 1 2.084554290102 110.95317716 45.93985291 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.238807759418 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.207e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40944 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10994 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1099 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24085 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9661887761935901 0.00e+00 4.53e-04 5.12e-03 1.06e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662316085644562 -4.28e-05 2.91e-04 3.24e-03 1.43e-03 0.1 + 3 -116.9662425807126027 -1.10e-05 8.74e-05 9.59e-04 3.18e-04 0.1 + 4 -116.9662433699806883 -7.89e-07 6.49e-06 3.65e-05 1.67e-05 0.1 + 5 -116.9662433732229516 -3.24e-09 2.52e-06 1.88e-05 1.23e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.095 sec) +Old exchange energy : -3.614443570 Eh +New exchange energy : -3.614491281 Eh +Exchange energy change after final integration : -0.000047710 Eh +Total energy after final integration : -116.966291084 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96629108368536 Eh -3182.81459 eV + +Components: +Nuclear Repulsion : 74.23880775941809 Eh 2020.14066 eV +Electronic Energy : -191.20505113264107 Eh -5202.95395 eV +One Electron Energy: -303.55066566463074 Eh -8260.03354 eV +Two Electron Energy: 112.34561453198968 Eh 3057.07959 eV + +Virial components: +Potential Energy : -232.15693371360885 Eh -6317.31133 eV +Kinetic Energy : 115.19064262992350 Eh 3134.49674 eV +Virial Ratio : 2.01541486715606 + +DFT components: +N(Alpha) : 12.999997965330 electrons +N(Beta) : 11.999998053112 electrons +N(Total) : 24.999996018442 electrons +E(X) : -14.265128635067 Eh +E(C) : -0.915676842510 Eh +E(XC) : -15.180805477577 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.2423e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.8835e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.5150e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7532e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.2327e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.8708e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754254 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004254 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966291083685 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000403696 0.000173962 0.000227185 + 2 C : 0.000094304 0.000610024 0.000139848 + 3 C : 0.000484024 0.000003463 -0.000129144 + 4 H : -0.000025645 -0.000232722 -0.000245307 + 5 H : -0.000033813 0.000067974 0.000034510 + 6 H : 0.000019761 -0.000123493 0.000128598 + 7 H : -0.000067573 -0.000269411 -0.000319557 + 8 H : -0.000074436 -0.000234278 -0.000229404 + 9 H : -0.000008103 -0.000032168 0.000236498 + 10 H : 0.000015176 0.000036648 0.000156773 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000247740 -0.0000229845 0.0000778144 + +Norm of the Cartesian gradient ... 0.0011941614 +RMS gradient ... 0.0002180230 +MAX gradient ... 0.0006100239 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.652 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.118 sec ( 18.1%) +COSX gradient .... 0.402 sec ( 61.7%) +XC gradient .... 0.126 sec ( 19.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966291084 Eh +Current gradient norm .... 0.001194161 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998603208 +Lowest eigenvalues of augmented Hessian: + -0.000018601 0.005835290 0.014083175 0.015467559 0.135757652 +Length of the computed step .... 0.052909803 +The final length of the internal step .... 0.052909803 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0090739563 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0071689308 RMS(Int)= 0.0090589960 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000009327 +Previously predicted energy change .... -0.000021462 +Actually observed energy change .... -0.000028488 +Ratio of predicted to observed change .... 1.327373585 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000284884 0.0000050000 NO + RMS gradient 0.0001724905 0.0001000000 NO + MAX gradient 0.0004763972 0.0003000000 NO + RMS step 0.0090739563 0.0020000000 NO + MAX step 0.0267179245 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.19 + Max(Dihed) 1.53 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5233 0.000476 -0.0004 1.5229 + 2. B(C 2,C 1) 1.5233 0.000473 -0.0004 1.5229 + 3. B(H 3,C 0) 1.1077 -0.000254 0.0002 1.1079 + 4. B(H 4,C 0) 1.1031 -0.000071 -0.0000 1.1031 + 5. B(H 5,C 0) 1.1015 -0.000135 0.0001 1.1015 + 6. B(H 6,C 1) 1.0987 -0.000209 0.0004 1.0991 + 7. B(H 7,C 2) 1.1077 -0.000245 0.0002 1.1079 + 8. B(H 8,C 2) 1.1015 -0.000142 0.0001 1.1015 + 9. B(H 9,C 2) 1.1031 -0.000074 -0.0000 1.1031 + 10. A(H 3,C 0,H 4) 107.00 -0.000154 -0.07 106.93 + 11. A(C 1,C 0,H 3) 111.79 0.000136 0.06 111.85 + 12. A(C 1,C 0,H 5) 111.09 0.000156 -0.02 111.07 + 13. A(H 4,C 0,H 5) 108.35 -0.000054 0.07 108.43 + 14. A(C 1,C 0,H 4) 110.93 -0.000008 -0.02 110.91 + 15. A(H 3,C 0,H 5) 107.48 -0.000095 -0.02 107.46 + 16. A(C 0,C 1,C 2) 120.77 -0.000100 -0.01 120.76 + 17. A(C 2,C 1,H 6) 118.24 0.000077 -0.19 118.05 + 18. A(C 0,C 1,H 6) 118.25 0.000052 -0.18 118.06 + 19. A(H 7,C 2,H 9) 106.97 -0.000204 -0.05 106.92 + 20. A(C 1,C 2,H 9) 110.95 -0.000001 -0.02 110.93 + 21. A(H 7,C 2,H 8) 107.44 -0.000113 -0.02 107.42 + 22. A(C 1,C 2,H 8) 111.11 0.000181 -0.03 111.08 + 23. A(H 8,C 2,H 9) 108.43 0.000013 0.05 108.48 + 24. A(C 1,C 2,H 7) 111.75 0.000105 0.07 111.82 + 25. D(C 2,C 1,C 0,H 4) -46.29 0.000017 0.13 -46.16 + 26. D(H 6,C 1,C 0,H 3) -87.83 -0.000208 1.47 -86.36 + 27. D(C 2,C 1,C 0,H 3) 73.06 -0.000093 0.06 73.12 + 28. D(H 6,C 1,C 0,H 4) 152.83 -0.000098 1.53 154.36 + 29. D(C 2,C 1,C 0,H 5) -166.88 -0.000015 0.06 -166.81 + 30. D(H 7,C 2,C 1,H 6) 87.54 0.000206 -1.50 86.04 + 31. D(H 7,C 2,C 1,C 0) -73.35 0.000096 -0.10 -73.45 + 32. D(H 9,C 2,C 1,C 0) 45.94 -0.000093 -0.14 45.80 + 33. D(H 8,C 2,C 1,H 6) -32.46 0.000155 -1.51 -33.97 + 34. D(H 8,C 2,C 1,C 0) 166.65 0.000045 -0.10 166.55 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (19.602 %) +Internal coordinates : 0.000 s ( 1.988 %) +B/P matrices and projection : 0.000 s (15.785 %) +Hessian update/contruction : 0.000 s (13.280 %) +Making the step : 0.000 s (11.571 %) +Converting the step to Cartesian: 0.000 s ( 2.147 %) +Storing new data : 0.000 s ( 1.789 %) +Checking convergence : 0.000 s ( 0.954 %) +Final printing : 0.001 s (32.763 %) +Total time : 0.003 s + +Time for energy+gradient : 5.491 s +Time for complete geometry iter : 6.343 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.330203 -0.017440 0.171967 + C 0.045962 0.463393 -0.268766 + C 1.286973 -0.378087 -0.002281 + H -1.460306 0.055445 1.269752 + H -1.483461 -1.075446 -0.100152 + H -2.127578 0.581432 -0.295900 + H 0.181337 1.537150 -0.460489 + H 1.576617 -0.357546 1.066919 + H 2.147124 -0.010776 -0.584170 + H 1.111167 -1.434416 -0.266976 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.513719 -0.032957 0.324971 + 1 C 6.0000 0 12.011 0.086855 0.875686 -0.507893 + 2 C 6.0000 0 12.011 2.432027 -0.714481 -0.004310 + 3 H 1.0000 0 1.008 -2.759578 0.104776 2.399483 + 4 H 1.0000 0 1.008 -2.803334 -2.032298 -0.189261 + 5 H 1.0000 0 1.008 -4.020540 1.098747 -0.559170 + 6 H 1.0000 0 1.008 0.342677 2.904793 -0.870199 + 7 H 1.0000 0 1.008 2.979375 -0.675664 2.016186 + 8 H 1.0000 0 1.008 4.057477 -0.020364 -1.103922 + 9 H 1.0000 0 1.008 2.099801 -2.710653 -0.504511 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522916559703 0.00000000 0.00000000 + C 2 1 0 1.522896154753 120.74894195 0.00000000 + H 1 2 3 1.107866922689 111.84606920 73.12222114 + H 1 2 3 1.103137808709 110.91403132 313.84228482 + H 1 2 3 1.101523482038 111.07264131 193.18637621 + H 2 1 3 1.099108566264 118.04926063 200.51297769 + H 3 2 1 1.107927957814 111.81824130 286.54605100 + H 3 2 1 1.101531694883 111.07829147 166.54548688 + H 3 2 1 1.103087503106 110.93230228 45.80282884 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.877895222652 0.00000000 0.00000000 + C 2 1 0 2.877856662885 120.74894195 0.00000000 + H 1 2 3 2.093565076713 111.84606920 73.12222114 + H 1 2 3 2.084628346434 110.91403132 313.84228482 + H 1 2 3 2.081577711136 111.07264131 193.18637621 + H 2 1 3 2.077014181686 118.04926063 200.51297769 + H 3 2 1 2.093680416384 111.81824130 286.54605100 + H 3 2 1 2.081593231163 111.07829147 166.54548688 + H 3 2 1 2.084533282622 110.93230228 45.80282884 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.253307174342 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.206e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40939 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5316 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10992 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1099 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24085 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9662084303599414 0.00e+00 4.00e-04 4.67e-03 8.76e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662457571764804 -3.73e-05 2.61e-04 2.96e-03 1.19e-03 0.1 + 3 -116.9662554739016542 -9.72e-06 8.02e-05 8.88e-04 2.63e-04 0.1 + 4 -116.9662561619631589 -6.88e-07 4.52e-06 3.20e-05 1.13e-05 0.1 + 5 -116.9662561639125755 -1.95e-09 1.53e-06 8.37e-06 5.75e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.614483136 Eh +New exchange energy : -3.614531139 Eh +Exchange energy change after final integration : -0.000048003 Eh +Total energy after final integration : -116.966304167 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96630416677830 Eh -3182.81495 eV + +Components: +Nuclear Repulsion : 74.25330717434245 Eh 2020.53521 eV +Electronic Energy : -191.21956333825503 Eh -5203.34885 eV +One Electron Energy: -303.57830103021467 Eh -8260.78554 eV +Two Electron Energy: 112.35873769195965 Eh 3057.43669 eV + +Virial components: +Potential Energy : -232.15812215004934 Eh -6317.34367 eV +Kinetic Energy : 115.19181798327104 Eh 3134.52872 eV +Virial Ratio : 2.01540462000318 + +DFT components: +N(Alpha) : 12.999997880561 electrons +N(Beta) : 11.999997872164 electrons +N(Total) : 24.999995752725 electrons +E(X) : -14.265254687301 Eh +E(C) : -0.915681259273 Eh +E(XC) : -15.180935946574 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9494e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.3729e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.5313e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6822e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.7514e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 5.6606e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754204 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004204 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.9 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966304166778 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000071535 0.000601227 0.000010404 + 2 C : -0.000039619 -0.000160028 -0.000225898 + 3 C : 0.000231651 0.000503606 -0.000230105 + 4 H : -0.000151258 -0.000384538 -0.000129247 + 5 H : 0.000065470 -0.000037295 0.000181769 + 6 H : 0.000067284 -0.000020063 0.000152163 + 7 H : -0.000029804 -0.000137013 -0.000148753 + 8 H : 0.000028115 -0.000399490 -0.000124523 + 9 H : -0.000027678 0.000060044 0.000239158 + 10 H : -0.000072628 -0.000026452 0.000275031 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000212210 -0.0000231122 0.0000778081 + +Norm of the Cartesian gradient ... 0.0011917438 +RMS gradient ... 0.0002175816 +MAX gradient ... 0.0006012273 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.643 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.116 sec ( 18.0%) +COSX gradient .... 0.402 sec ( 62.5%) +XC gradient .... 0.120 sec ( 18.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966304167 Eh +Current gradient norm .... 0.001191744 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998141012 +Lowest eigenvalues of augmented Hessian: + -0.000015184 0.003048479 0.014083177 0.017240214 0.136253731 +Length of the computed step .... 0.061060371 +The final length of the internal step .... 0.061060371 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0104717672 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0096918979 RMS(Int)= 0.0104606428 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000007620 +Previously predicted energy change .... -0.000009327 +Actually observed energy change .... -0.000013083 +Ratio of predicted to observed change .... 1.402748946 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000130831 0.0000050000 NO + RMS gradient 0.0001599011 0.0001000000 NO + MAX gradient 0.0003814219 0.0003000000 NO + RMS step 0.0104717672 0.0020000000 NO + MAX step 0.0291142139 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.17 + Max(Dihed) 1.67 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5229 0.000091 -0.0003 1.5226 + 2. B(C 2,C 1) 1.5229 0.000084 -0.0003 1.5226 + 3. B(H 3,C 0) 1.1079 -0.000135 0.0002 1.1081 + 4. B(H 4,C 0) 1.1031 -0.000020 -0.0001 1.1031 + 5. B(H 5,C 0) 1.1015 -0.000124 0.0002 1.1017 + 6. B(H 6,C 1) 1.0991 -0.000112 0.0004 1.0995 + 7. B(H 7,C 2) 1.1079 -0.000121 0.0002 1.1081 + 8. B(H 8,C 2) 1.1015 -0.000129 0.0002 1.1017 + 9. B(H 9,C 2) 1.1031 -0.000027 -0.0001 1.1030 + 10. A(H 3,C 0,H 4) 106.93 -0.000324 0.05 106.98 + 11. A(C 1,C 0,H 3) 111.85 0.000378 -0.02 111.82 + 12. A(C 1,C 0,H 5) 111.07 0.000056 -0.04 111.03 + 13. A(H 4,C 0,H 5) 108.43 0.000080 0.02 108.45 + 14. A(C 1,C 0,H 4) 110.91 -0.000099 0.01 110.93 + 15. A(H 3,C 0,H 5) 107.46 -0.000110 -0.02 107.44 + 16. A(C 0,C 1,C 2) 120.75 0.000045 -0.02 120.73 + 17. A(C 2,C 1,H 6) 118.03 -0.000021 -0.17 117.86 + 18. A(C 0,C 1,H 6) 118.05 -0.000036 -0.16 117.89 + 19. A(H 7,C 2,H 9) 106.92 -0.000381 0.07 106.99 + 20. A(C 1,C 2,H 9) 110.93 -0.000084 0.01 110.94 + 21. A(H 7,C 2,H 8) 107.43 -0.000142 -0.01 107.42 + 22. A(C 1,C 2,H 8) 111.08 0.000090 -0.05 111.03 + 23. A(H 8,C 2,H 9) 108.48 0.000170 -0.02 108.47 + 24. A(C 1,C 2,H 7) 111.82 0.000328 -0.00 111.81 + 25. D(C 2,C 1,C 0,H 4) -46.16 0.000010 0.48 -45.68 + 26. D(H 6,C 1,C 0,H 3) -86.36 -0.000173 1.65 -84.72 + 27. D(C 2,C 1,C 0,H 3) 73.12 -0.000215 0.53 73.66 + 28. D(H 6,C 1,C 0,H 4) 154.36 0.000053 1.59 155.94 + 29. D(C 2,C 1,C 0,H 5) -166.81 -0.000061 0.47 -166.35 + 30. D(H 7,C 2,C 1,H 6) 86.04 0.000156 -1.67 84.37 + 31. D(H 7,C 2,C 1,C 0) -73.45 0.000202 -0.56 -74.01 + 32. D(H 9,C 2,C 1,C 0) 45.80 -0.000120 -0.46 45.34 + 33. D(H 8,C 2,C 1,H 6) -33.96 0.000054 -1.62 -35.59 + 34. D(H 8,C 2,C 1,C 0) 166.55 0.000100 -0.51 166.03 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (21.586 %) +Internal coordinates : 0.000 s ( 1.871 %) +B/P matrices and projection : 0.000 s (14.179 %) +Hessian update/contruction : 0.000 s (13.131 %) +Making the step : 0.000 s (11.298 %) +Converting the step to Cartesian: 0.000 s ( 2.282 %) +Storing new data : 0.000 s ( 1.758 %) +Checking convergence : 0.000 s ( 0.748 %) +Final printing : 0.001 s (32.997 %) +Total time : 0.003 s + +Time for energy+gradient : 5.384 s +Time for complete geometry iter : 6.433 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.330080 -0.018256 0.169791 + C 0.045888 0.463357 -0.269660 + C 1.286320 -0.378748 -0.004099 + H -1.463565 0.061779 1.266892 + H -1.480162 -1.078129 -0.096525 + H -2.127162 0.576551 -0.304150 + H 0.183187 1.540747 -0.440792 + H 1.581293 -0.352041 1.063703 + H 2.144081 -0.015505 -0.592414 + H 1.107832 -1.436046 -0.262842 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.513487 -0.034498 0.320858 + 1 C 6.0000 0 12.011 0.086716 0.875618 -0.509583 + 2 C 6.0000 0 12.011 2.430793 -0.715730 -0.007746 + 3 H 1.0000 0 1.008 -2.765738 0.116746 2.394079 + 4 H 1.0000 0 1.008 -2.797101 -2.037368 -0.182406 + 5 H 1.0000 0 1.008 -4.019753 1.089523 -0.574761 + 6 H 1.0000 0 1.008 0.346174 2.911591 -0.832975 + 7 H 1.0000 0 1.008 2.988212 -0.665261 2.010108 + 8 H 1.0000 0 1.008 4.051726 -0.029300 -1.119501 + 9 H 1.0000 0 1.008 2.093499 -2.713734 -0.496699 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522614662904 0.00000000 0.00000000 + C 2 1 0 1.522608124670 120.72616179 0.00000000 + H 1 2 3 1.108086114646 111.82488245 73.65710785 + H 1 2 3 1.103077556296 110.92777808 314.31898938 + H 1 2 3 1.101705288766 111.03170937 193.65362721 + H 2 1 3 1.099503052817 117.88598906 201.62330426 + H 3 2 1 1.108117364708 111.81420373 285.98675517 + H 3 2 1 1.101732605312 111.02586703 166.03205759 + H 3 2 1 1.103034582480 110.94034406 45.33913600 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.877324720381 0.00000000 0.00000000 + C 2 1 0 2.877312364910 120.72616179 0.00000000 + H 1 2 3 2.093979289482 111.82488245 73.65710785 + H 1 2 3 2.084514485875 110.92777808 314.31898938 + H 1 2 3 2.081921276061 111.03170937 193.65362721 + H 2 1 3 2.077759653235 117.88598906 201.62330426 + H 3 2 1 2.094038343540 111.81420373 285.98675517 + H 3 2 1 2.081972896850 111.02586703 166.03205759 + H 3 2 1 2.084433277132 110.94034406 45.33913600 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.263655885175 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.205e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40936 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5316 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10995 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24081 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9662040645532812 0.00e+00 4.26e-04 4.69e-03 7.69e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662538016061291 -4.97e-05 2.75e-04 3.00e-03 1.09e-03 0.1 + 3 -116.9662659101685591 -1.21e-05 8.47e-05 9.11e-04 2.89e-04 0.1 + 4 -116.9662667124990065 -8.02e-07 5.24e-06 2.91e-05 1.55e-05 0.1 + 5 -116.9662667163789109 -3.88e-09 2.03e-06 1.19e-05 7.20e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.095 sec) +Old exchange energy : -3.614496199 Eh +New exchange energy : -3.614544821 Eh +Exchange energy change after final integration : -0.000048621 Eh +Total energy after final integration : -116.966315338 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96631533762292 Eh -3182.81525 eV + +Components: +Nuclear Repulsion : 74.26365588517531 Eh 2020.81681 eV +Electronic Energy : -191.22992260155422 Eh -5203.63074 eV +One Electron Energy: -303.59835124057372 Eh -8261.33114 eV +Two Electron Energy: 112.36842863901951 Eh 3057.70039 eV + +Virial components: +Potential Energy : -232.15892589113994 Eh -6317.36554 eV +Kinetic Energy : 115.19261055351703 Eh 3134.55029 eV +Virial Ratio : 2.01539773059733 + +DFT components: +N(Alpha) : 12.999997963987 electrons +N(Beta) : 11.999997841667 electrons +N(Total) : 24.999995805653 electrons +E(X) : -14.265287619602 Eh +E(C) : -0.915677710590 Eh +E(XC) : -15.180965330191 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.8799e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.1853e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0318e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.7918e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.1961e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.3895e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754165 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004165 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.0 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966315337623 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000233955 0.000633720 -0.000069239 + 2 C : -0.000124330 -0.000649455 -0.000411279 + 3 C : -0.000077746 0.000641369 -0.000116203 + 4 H : -0.000139323 -0.000331570 0.000021528 + 5 H : 0.000078158 -0.000092038 0.000160408 + 6 H : 0.000068337 0.000064079 0.000089477 + 7 H : 0.000009977 0.000029125 -0.000007723 + 8 H : 0.000053941 -0.000336121 0.000020609 + 9 H : -0.000026352 0.000103463 0.000124038 + 10 H : -0.000076617 -0.000062572 0.000188384 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000167493 -0.0000242537 0.0000811401 + +Norm of the Cartesian gradient ... 0.0013692021 +RMS gradient ... 0.0002499810 +MAX gradient ... 0.0006494549 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.651 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.116 sec ( 17.9%) +COSX gradient .... 0.410 sec ( 63.0%) +XC gradient .... 0.119 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966315338 Eh +Current gradient norm .... 0.001369202 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.996799119 +Lowest eigenvalues of augmented Hessian: + -0.000016873 0.001774926 0.014083189 0.017923281 0.130190064 +Length of the computed step .... 0.080203676 +The final length of the internal step .... 0.080203676 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0137548169 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0142639756 RMS(Int)= 0.0137493440 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000008491 +Previously predicted energy change .... -0.000007620 +Actually observed energy change .... -0.000011171 +Ratio of predicted to observed change .... 1.465948360 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000111708 0.0000050000 NO + RMS gradient 0.0001487861 0.0001000000 NO + MAX gradient 0.0003461738 0.0003000000 NO + RMS step 0.0137548169 0.0020000000 NO + MAX step 0.0334134706 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.17 + Max(Dihed) 1.91 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5226 -0.000249 0.0000 1.5226 + 2. B(C 2,C 1) 1.5226 -0.000254 0.0000 1.5226 + 3. B(H 3,C 0) 1.1081 0.000015 0.0002 1.1082 + 4. B(H 4,C 0) 1.1031 0.000037 -0.0002 1.1029 + 5. B(H 5,C 0) 1.1017 -0.000053 0.0003 1.1020 + 6. B(H 6,C 1) 1.0995 0.000031 0.0003 1.0998 + 7. B(H 7,C 2) 1.1081 0.000025 0.0001 1.1082 + 8. B(H 8,C 2) 1.1017 -0.000053 0.0003 1.1020 + 9. B(H 9,C 2) 1.1030 0.000030 -0.0001 1.1029 + 10. A(H 3,C 0,H 4) 106.98 -0.000280 0.14 107.12 + 11. A(C 1,C 0,H 3) 111.82 0.000346 -0.08 111.74 + 12. A(C 1,C 0,H 5) 111.03 -0.000048 -0.05 110.98 + 13. A(H 4,C 0,H 5) 108.45 0.000120 -0.02 108.43 + 14. A(C 1,C 0,H 4) 110.93 -0.000101 0.04 110.97 + 15. A(H 3,C 0,H 5) 107.44 -0.000048 -0.03 107.41 + 16. A(C 0,C 1,C 2) 120.73 0.000069 -0.00 120.72 + 17. A(C 2,C 1,H 6) 117.86 -0.000059 -0.13 117.73 + 18. A(C 0,C 1,H 6) 117.89 -0.000054 -0.13 117.75 + 19. A(H 7,C 2,H 9) 106.99 -0.000308 0.17 107.16 + 20. A(C 1,C 2,H 9) 110.94 -0.000085 0.03 110.97 + 21. A(H 7,C 2,H 8) 107.42 -0.000072 -0.01 107.41 + 22. A(C 1,C 2,H 8) 111.03 -0.000027 -0.06 110.97 + 23. A(H 8,C 2,H 9) 108.47 0.000175 -0.06 108.41 + 24. A(C 1,C 2,H 7) 111.81 0.000307 -0.06 111.75 + 25. D(C 2,C 1,C 0,H 4) -45.68 -0.000037 1.04 -44.64 + 26. D(H 6,C 1,C 0,H 3) -84.72 -0.000087 1.90 -82.82 + 27. D(C 2,C 1,C 0,H 3) 73.66 -0.000229 1.19 74.85 + 28. D(H 6,C 1,C 0,H 4) 155.94 0.000105 1.75 157.69 + 29. D(C 2,C 1,C 0,H 5) -166.35 -0.000089 1.06 -165.28 + 30. D(H 7,C 2,C 1,H 6) 84.37 0.000071 -1.91 82.45 + 31. D(H 7,C 2,C 1,C 0) -74.01 0.000212 -1.21 -75.22 + 32. D(H 9,C 2,C 1,C 0) 45.34 -0.000032 -1.02 44.32 + 33. D(H 8,C 2,C 1,H 6) -35.59 -0.000026 -1.82 -37.41 + 34. D(H 8,C 2,C 1,C 0) 166.03 0.000115 -1.11 164.92 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (23.445 %) +Internal coordinates : 0.000 s ( 1.885 %) +B/P matrices and projection : 0.000 s (14.248 %) +Hessian update/contruction : 0.000 s (11.986 %) +Making the step : 0.000 s (10.818 %) +Converting the step to Cartesian: 0.000 s ( 2.111 %) +Storing new data : 0.000 s ( 1.922 %) +Checking convergence : 0.000 s ( 0.716 %) +Final printing : 0.001 s (32.755 %) +Total time : 0.003 s + +Time for energy+gradient : 5.263 s +Time for complete geometry iter : 6.083 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.330504 -0.019460 0.167410 + C 0.046403 0.465239 -0.265715 + C 1.286083 -0.379904 -0.006140 + H -1.471777 0.071130 1.262872 + H -1.474535 -1.081749 -0.091860 + H -2.126405 0.568550 -0.317468 + H 0.185633 1.545967 -0.414830 + H 1.591339 -0.345104 1.058649 + H 2.139190 -0.023043 -0.605543 + H 1.102206 -1.437917 -0.257470 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.514288 -0.036775 0.316358 + 1 C 6.0000 0 12.011 0.087689 0.879174 -0.502128 + 2 C 6.0000 0 12.011 2.430345 -0.717915 -0.011603 + 3 H 1.0000 0 1.008 -2.781256 0.134417 2.386482 + 4 H 1.0000 0 1.008 -2.786467 -2.044210 -0.173591 + 5 H 1.0000 0 1.008 -4.018323 1.074404 -0.599927 + 6 H 1.0000 0 1.008 0.350795 2.921455 -0.783916 + 7 H 1.0000 0 1.008 3.007194 -0.652152 2.000556 + 8 H 1.0000 0 1.008 4.042483 -0.043545 -1.144310 + 9 H 1.0000 0 1.008 2.082868 -2.717270 -0.486549 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522630493762 0.00000000 0.00000000 + C 2 1 0 1.522646430115 120.73448233 0.00000000 + H 1 2 3 1.108242927606 111.74221779 74.84939866 + H 1 2 3 1.102916102887 110.96682013 315.35750945 + H 1 2 3 1.101962048273 110.98399641 194.71792564 + H 2 1 3 1.099815842896 117.76530177 202.33095508 + H 3 2 1 1.108226856813 111.75393635 284.77834849 + H 3 2 1 1.102009111392 110.96560784 164.91847599 + H 3 2 1 1.102891450621 110.96973754 44.32160191 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.877354636368 0.00000000 0.00000000 + C 2 1 0 2.877384751710 120.73448233 0.00000000 + H 1 2 3 2.094275623031 111.74221779 74.84939866 + H 1 2 3 2.084209383148 110.96682013 315.35750945 + H 1 2 3 2.082406481210 110.98399641 194.71792564 + H 2 1 3 2.078350740822 117.76530177 202.33095508 + H 3 2 1 2.094245253633 111.75393635 284.77834849 + H 3 2 1 2.082495417617 110.96560784 164.91847599 + H 3 2 1 2.084162797117 110.96973754 44.32160191 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.262973055743 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.205e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40933 +Total number of batches ... 646 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5316 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10998 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24077 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9661637537432313 0.00e+00 5.42e-04 4.83e-03 1.00e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662569631882576 -9.32e-05 3.30e-04 3.13e-03 1.43e-03 0.1 + 3 -116.9662764316433794 -1.95e-05 9.76e-05 9.60e-04 3.77e-04 0.1 + 4 -116.9662775619082851 -1.13e-06 7.16e-06 4.50e-05 2.47e-05 0.1 + 5 -116.9662775709270335 -9.02e-09 2.69e-06 1.53e-05 7.28e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.614474724 Eh +New exchange energy : -3.614524389 Eh +Exchange energy change after final integration : -0.000049665 Eh +Total energy after final integration : -116.966327236 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96632723642379 Eh -3182.81558 eV + +Components: +Nuclear Repulsion : 74.26297305574256 Eh 2020.79823 eV +Electronic Energy : -191.22925062666960 Eh -5203.61246 eV +One Electron Energy: -303.59719181936453 Eh -8261.29959 eV +Two Electron Energy: 112.36794119269493 Eh 3057.68713 eV + +Virial components: +Potential Energy : -232.15905547649811 Eh -6317.36907 eV +Kinetic Energy : 115.19272824007433 Eh 3134.55349 eV +Virial Ratio : 2.01539679651178 + +DFT components: +N(Alpha) : 12.999998336340 electrons +N(Beta) : 11.999998054500 electrons +N(Total) : 24.999996390840 electrons +E(X) : -14.265202379622 Eh +E(C) : -0.915662846827 Eh +E(XC) : -15.180865226449 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.0187e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.5256e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.6916e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.2034e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.2784e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.1948e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754140 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004140 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966327236424 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000332273 0.000313431 -0.000026325 + 2 C : -0.000140452 -0.000703518 -0.000437776 + 3 C : -0.000254201 0.000404744 0.000136060 + 4 H : -0.000022531 -0.000120103 0.000138992 + 5 H : 0.000024610 -0.000083238 0.000030067 + 6 H : 0.000042395 0.000100994 -0.000008365 + 7 H : 0.000039471 0.000162344 0.000096489 + 8 H : 0.000013354 -0.000101283 0.000134686 + 9 H : -0.000021165 0.000086286 -0.000040469 + 10 H : -0.000013754 -0.000059656 -0.000023360 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000105778 -0.0000265496 0.0000870961 + +Norm of the Cartesian gradient ... 0.0011388502 +RMS gradient ... 0.0002079246 +MAX gradient ... 0.0007035182 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.650 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 17.9%) +COSX gradient .... 0.409 sec ( 62.9%) +XC gradient .... 0.119 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966327236 Eh +Current gradient norm .... 0.001138850 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.997340059 +Lowest eigenvalues of augmented Hessian: + -0.000012838 0.001299269 0.014082665 0.014420370 0.129609143 +Length of the computed step .... 0.073083394 +The final length of the internal step .... 0.073083394 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0125336987 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0140533472 RMS(Int)= 0.0125385698 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000006453 +Previously predicted energy change .... -0.000008491 +Actually observed energy change .... -0.000011899 +Ratio of predicted to observed change .... 1.401415322 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000118988 0.0000050000 NO + RMS gradient 0.0001228191 0.0001000000 NO + MAX gradient 0.0003721634 0.0003000000 NO + RMS step 0.0125336987 0.0020000000 NO + MAX step 0.0252627399 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.14 + Max(Dihed) 1.45 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5226 -0.000372 0.0003 1.5229 + 2. B(C 2,C 1) 1.5226 -0.000370 0.0003 1.5230 + 3. B(H 3,C 0) 1.1082 0.000131 -0.0000 1.1082 + 4. B(H 4,C 0) 1.1029 0.000067 -0.0002 1.1027 + 5. B(H 5,C 0) 1.1020 0.000028 0.0002 1.1022 + 6. B(H 6,C 1) 1.0998 0.000151 0.0000 1.0998 + 7. B(H 7,C 2) 1.1082 0.000129 -0.0000 1.1082 + 8. B(H 8,C 2) 1.1020 0.000033 0.0002 1.1022 + 9. B(H 9,C 2) 1.1029 0.000067 -0.0002 1.1027 + 10. A(H 3,C 0,H 4) 107.12 -0.000080 0.14 107.26 + 11. A(C 1,C 0,H 3) 111.74 0.000093 -0.08 111.67 + 12. A(C 1,C 0,H 5) 110.98 -0.000118 -0.02 110.96 + 13. A(H 4,C 0,H 5) 108.43 0.000080 -0.03 108.40 + 14. A(C 1,C 0,H 4) 110.97 -0.000023 0.03 111.00 + 15. A(H 3,C 0,H 5) 107.41 0.000052 -0.04 107.38 + 16. A(C 0,C 1,C 2) 120.73 0.000026 0.05 120.79 + 17. A(C 2,C 1,H 6) 117.74 -0.000055 -0.02 117.72 + 18. A(C 0,C 1,H 6) 117.77 -0.000027 -0.03 117.74 + 19. A(H 7,C 2,H 9) 107.16 -0.000061 0.14 107.30 + 20. A(C 1,C 2,H 9) 110.97 -0.000016 0.02 110.99 + 21. A(H 7,C 2,H 8) 107.41 0.000051 -0.02 107.39 + 22. A(C 1,C 2,H 8) 110.97 -0.000123 -0.03 110.94 + 23. A(H 8,C 2,H 9) 108.41 0.000061 -0.05 108.36 + 24. A(C 1,C 2,H 7) 111.75 0.000093 -0.06 111.69 + 25. D(C 2,C 1,C 0,H 4) -44.64 -0.000093 1.30 -43.35 + 26. D(H 6,C 1,C 0,H 3) -82.82 0.000024 1.31 -81.51 + 27. D(C 2,C 1,C 0,H 3) 74.85 -0.000148 1.44 76.29 + 28. D(H 6,C 1,C 0,H 4) 157.69 0.000079 1.17 158.86 + 29. D(C 2,C 1,C 0,H 5) -165.28 -0.000099 1.33 -163.95 + 30. D(H 7,C 2,C 1,H 6) 82.45 -0.000030 -1.32 81.13 + 31. D(H 7,C 2,C 1,C 0) -75.22 0.000136 -1.45 -76.67 + 32. D(H 9,C 2,C 1,C 0) 44.32 0.000109 -1.29 43.03 + 33. D(H 8,C 2,C 1,H 6) -37.41 -0.000074 -1.23 -38.63 + 34. D(H 8,C 2,C 1,C 0) 164.92 0.000093 -1.35 163.56 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (23.271 %) +Internal coordinates : 0.000 s ( 1.919 %) +B/P matrices and projection : 0.000 s (15.194 %) +Hessian update/contruction : 0.000 s (11.755 %) +Making the step : 0.000 s (11.795 %) +Converting the step to Cartesian: 0.000 s ( 2.079 %) +Storing new data : 0.000 s ( 1.679 %) +Checking convergence : 0.000 s ( 0.720 %) +Final printing : 0.001 s (31.467 %) +Total time : 0.003 s + +Time for energy+gradient : 5.298 s +Time for complete geometry iter : 6.154 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 8 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.331441 -0.020362 0.165816 + C 0.047408 0.468498 -0.257449 + C 1.286559 -0.380945 -0.007666 + H -1.483173 0.079506 1.259059 + H -1.468319 -1.084785 -0.087678 + H -2.125414 0.560514 -0.331106 + H 0.187704 1.550890 -0.393066 + H 1.604086 -0.340065 1.053271 + H 2.134162 -0.030406 -0.618852 + H 1.096061 -1.439135 -0.252424 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.516059 -0.038479 0.313346 + 1 C 6.0000 0 12.011 0.089587 0.885333 -0.486507 + 2 C 6.0000 0 12.011 2.431244 -0.719882 -0.014487 + 3 H 1.0000 0 1.008 -2.802792 0.150244 2.379277 + 4 H 1.0000 0 1.008 -2.774720 -2.049946 -0.165687 + 5 H 1.0000 0 1.008 -4.016450 1.059218 -0.625701 + 6 H 1.0000 0 1.008 0.354710 2.930757 -0.742786 + 7 H 1.0000 0 1.008 3.031283 -0.642630 1.990393 + 8 H 1.0000 0 1.008 4.032982 -0.057460 -1.169462 + 9 H 1.0000 0 1.008 2.071255 -2.719570 -0.477012 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522944556412 0.00000000 0.00000000 + C 2 1 0 1.522970796101 120.79961213 0.00000000 + H 1 2 3 1.108231724462 111.66624559 76.29173415 + H 1 2 3 1.102718996666 110.99842115 316.65361936 + H 1 2 3 1.102153604256 110.96141535 196.04776540 + H 2 1 3 1.099839589547 117.75333133 202.20413104 + H 3 2 1 1.108188569309 111.68927461 283.33218089 + H 3 2 1 1.102205676775 110.93845772 163.56475150 + H 3 2 1 1.102706042588 110.99419035 43.03096831 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.877948128765 0.00000000 0.00000000 + C 2 1 0 2.877997714590 120.79961213 0.00000000 + H 1 2 3 2.094254452156 111.66624559 76.29173415 + H 1 2 3 2.083836906371 110.99842115 316.65361936 + H 1 2 3 2.082768469557 110.96141535 196.04776540 + H 2 1 3 2.078395615489 117.75333133 202.20413104 + H 3 2 1 2.094172900737 111.68927461 283.33218089 + H 3 2 1 2.082866872358 110.93845772 163.56475150 + H 3 2 1 2.083812426711 110.99419035 43.03096831 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.250238366866 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.206e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40930 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10998 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24069 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2407 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9661796467975563 0.00e+00 5.15e-04 2.80e-03 8.26e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662695628134514 -8.99e-05 2.84e-04 1.86e-03 1.18e-03 0.1 + 3 -116.9662848790543279 -1.53e-05 7.51e-05 6.04e-04 3.10e-04 0.1 + 4 -116.9662855934737848 -7.14e-07 7.41e-06 5.29e-05 2.61e-05 0.1 + 5 -116.9662856034653799 -9.99e-09 1.69e-06 8.23e-06 5.30e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.099 sec) +Old exchange energy : -3.614431978 Eh +New exchange energy : -3.614482539 Eh +Exchange energy change after final integration : -0.000050561 Eh +Total energy after final integration : -116.966336165 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96633616482609 Eh -3182.81582 eV + +Components: +Nuclear Repulsion : 74.25023836686616 Eh 2020.45170 eV +Electronic Energy : -191.21652397033154 Eh -5203.26615 eV +One Electron Energy: -303.57245263250189 Eh -8260.62640 eV +Two Electron Energy: 112.35592866217034 Eh 3057.36025 eV + +Virial components: +Potential Energy : -232.15844288597395 Eh -6317.35240 eV +Kinetic Energy : 115.19210672114787 Eh 3134.53658 eV +Virial Ratio : 2.01540235259325 + +DFT components: +N(Alpha) : 12.999998823807 electrons +N(Beta) : 11.999998399399 electrons +N(Total) : 24.999997223206 electrons +E(X) : -14.265053790248 Eh +E(C) : -0.915647690381 Eh +E(XC) : -15.180701480630 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 9.9916e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.2331e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6945e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.8252e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.3047e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0660e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754147 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004147 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.2 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966336164826 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000141224 -0.000113127 0.000075911 + 2 C : -0.000073646 -0.000300564 -0.000273067 + 3 C : -0.000158919 -0.000024605 0.000303083 + 4 H : 0.000102364 0.000088783 0.000133931 + 5 H : -0.000039599 -0.000024227 -0.000096042 + 6 H : 0.000006173 0.000072453 -0.000063714 + 7 H : 0.000037013 0.000166352 0.000096897 + 8 H : -0.000054354 0.000124587 0.000132980 + 9 H : -0.000014136 0.000029012 -0.000127075 + 10 H : 0.000053879 -0.000018665 -0.000182904 + +Difference to translation invariance: + : -0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000094622 -0.0000307752 0.0000957245 + +Norm of the Cartesian gradient ... 0.0007155859 +RMS gradient ... 0.0001306475 +MAX gradient ... 0.0003030832 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.652 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.127 sec ( 19.5%) +COSX gradient .... 0.399 sec ( 61.2%) +XC gradient .... 0.120 sec ( 18.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966336165 Eh +Current gradient norm .... 0.000715586 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998519170 +Lowest eigenvalues of augmented Hessian: + -0.000007530 0.001081430 0.009476983 0.014084144 0.134228529 +Length of the computed step .... 0.054481660 +The final length of the internal step .... 0.054481660 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0093435275 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0108902345 RMS(Int)= 0.0093503057 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000003776 +Previously predicted energy change .... -0.000006453 +Actually observed energy change .... -0.000008928 +Ratio of predicted to observed change .... 1.383580652 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000089284 0.0000050000 NO + RMS gradient 0.0001036070 0.0001000000 NO + MAX gradient 0.0001867795 0.0003000000 YES + RMS step 0.0093435275 0.0020000000 NO + MAX step 0.0210996608 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0003 Max(Angles) 0.09 + Max(Dihed) 1.21 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5229 -0.000187 0.0003 1.5232 + 2. B(C 2,C 1) 1.5230 -0.000179 0.0003 1.5232 + 3. B(H 3,C 0) 1.1082 0.000127 -0.0001 1.1081 + 4. B(H 4,C 0) 1.1027 0.000048 -0.0001 1.1026 + 5. B(H 5,C 0) 1.1022 0.000063 0.0001 1.1022 + 6. B(H 6,C 1) 1.0998 0.000156 -0.0002 1.0997 + 7. B(H 7,C 2) 1.1082 0.000115 -0.0001 1.1081 + 8. B(H 8,C 2) 1.1022 0.000068 0.0001 1.1023 + 9. B(H 9,C 2) 1.1027 0.000052 -0.0001 1.1026 + 10. A(H 3,C 0,H 4) 107.26 0.000116 0.05 107.31 + 11. A(C 1,C 0,H 3) 111.67 -0.000182 -0.01 111.66 + 12. A(C 1,C 0,H 5) 110.96 -0.000099 0.01 110.97 + 13. A(H 4,C 0,H 5) 108.40 0.000004 -0.01 108.39 + 14. A(C 1,C 0,H 4) 111.00 0.000067 -0.00 111.00 + 15. A(H 3,C 0,H 5) 107.38 0.000106 -0.03 107.34 + 16. A(C 0,C 1,C 2) 120.80 -0.000033 0.09 120.89 + 17. A(C 2,C 1,H 6) 117.73 -0.000018 0.05 117.78 + 18. A(C 0,C 1,H 6) 117.75 0.000013 0.04 117.79 + 19. A(H 7,C 2,H 9) 107.30 0.000162 0.04 107.34 + 20. A(C 1,C 2,H 9) 110.99 0.000061 -0.00 110.99 + 21. A(H 7,C 2,H 8) 107.39 0.000129 -0.04 107.35 + 22. A(C 1,C 2,H 8) 110.94 -0.000126 0.01 110.95 + 23. A(H 8,C 2,H 9) 108.36 -0.000067 0.00 108.36 + 24. A(C 1,C 2,H 7) 111.69 -0.000146 -0.01 111.68 + 25. D(C 2,C 1,C 0,H 4) -43.35 -0.000102 1.15 -42.20 + 26. D(H 6,C 1,C 0,H 3) -81.50 0.000079 0.63 -80.87 + 27. D(C 2,C 1,C 0,H 3) 76.29 -0.000032 1.21 77.50 + 28. D(H 6,C 1,C 0,H 4) 158.86 0.000008 0.57 159.43 + 29. D(C 2,C 1,C 0,H 5) -163.95 -0.000086 1.16 -162.79 + 30. D(H 7,C 2,C 1,H 6) 81.13 -0.000076 -0.63 80.51 + 31. D(H 7,C 2,C 1,C 0) -76.67 0.000028 -1.20 -77.87 + 32. D(H 9,C 2,C 1,C 0) 43.03 0.000177 -1.16 41.87 + 33. D(H 8,C 2,C 1,H 6) -38.63 -0.000056 -0.58 -39.21 + 34. D(H 8,C 2,C 1,C 0) 163.56 0.000048 -1.15 162.41 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (22.902 %) +Internal coordinates : 0.000 s ( 2.425 %) +B/P matrices and projection : 0.000 s (14.665 %) +Hessian update/contruction : 0.000 s (12.356 %) +Making the step : 0.000 s (11.085 %) +Converting the step to Cartesian: 0.000 s ( 2.425 %) +Storing new data : 0.000 s ( 1.694 %) +Checking convergence : 0.000 s ( 0.770 %) +Final printing : 0.001 s (31.563 %) +Total time : 0.003 s + +Time for energy+gradient : 5.305 s +Time for complete geometry iter : 6.173 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 9 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.332351 -0.020646 0.165037 + C 0.048435 0.471664 -0.248748 + C 1.287287 -0.381455 -0.008645 + H -1.494144 0.084879 1.256198 + H -1.462885 -1.086659 -0.084451 + H -2.124371 0.554523 -0.341684 + H 0.189055 1.554470 -0.379192 + H 1.615601 -0.337861 1.048791 + H 2.130220 -0.035661 -0.629032 + H 1.090785 -1.439546 -0.248371 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.517778 -0.039015 0.311875 + 1 C 6.0000 0 12.011 0.091528 0.891316 -0.470066 + 2 C 6.0000 0 12.011 2.432621 -0.720845 -0.016336 + 3 H 1.0000 0 1.008 -2.823523 0.160398 2.373870 + 4 H 1.0000 0 1.008 -2.764452 -2.053488 -0.159590 + 5 H 1.0000 0 1.008 -4.014479 1.047897 -0.645688 + 6 H 1.0000 0 1.008 0.357262 2.937523 -0.716568 + 7 H 1.0000 0 1.008 3.053044 -0.638464 1.981929 + 8 H 1.0000 0 1.008 4.025533 -0.067389 -1.188698 + 9 H 1.0000 0 1.008 2.061285 -2.720347 -0.469353 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.523205649960 0.00000000 0.00000000 + C 2 1 0 1.523226184173 120.89216824 0.00000000 + H 1 2 3 1.108126186291 111.65835858 77.49997504 + H 1 2 3 1.102573156587 110.99833096 317.80357339 + H 1 2 3 1.102216716098 110.96746767 197.21219659 + H 2 1 3 1.099663062471 117.80055951 201.62827431 + H 3 2 1 1.108089258284 111.67628836 282.13046561 + H 3 2 1 1.102265546822 110.94916380 162.41121892 + H 3 2 1 1.102559747570 110.99343210 41.86971566 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.878441524066 0.00000000 0.00000000 + C 2 1 0 2.878480328105 120.89216824 0.00000000 + H 1 2 3 2.094055013916 111.65835858 77.49997504 + H 1 2 3 2.083561308562 110.99833096 317.80357339 + H 1 2 3 2.082887733655 110.96746767 197.21219659 + H 2 1 3 2.078062027659 117.80055951 201.62827431 + H 3 2 1 2.093985230097 111.67628836 282.13046561 + H 3 2 1 2.082980010350 110.94916380 162.41121892 + H 3 2 1 2.083535969193 110.99343210 41.86971566 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.237357784032 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.207e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40934 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 47 +Average number of points per batch ... 113 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10997 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24072 +Total number of batches ... 195 +Average number of points per batch ... 123 +Average number of grid points per atom ... 2407 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9662235204058760 0.00e+00 4.16e-04 2.09e-03 5.97e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662814164603191 -5.79e-05 2.12e-04 1.07e-03 7.92e-04 0.1 + 3 -116.9662898531179991 -8.44e-06 4.87e-05 3.41e-04 1.90e-04 0.1 + 4 -116.9662901675147708 -3.14e-07 6.48e-06 4.12e-05 2.11e-05 0.1 + 5 -116.9662901742214132 -6.71e-09 1.23e-06 6.02e-06 4.27e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.614406659 Eh +New exchange energy : -3.614457677 Eh +Exchange energy change after final integration : -0.000051018 Eh +Total energy after final integration : -116.966341192 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96634119237650 Eh -3182.81596 eV + +Components: +Nuclear Repulsion : 74.23735778403177 Eh 2020.10121 eV +Electronic Energy : -191.20364795825316 Eh -5202.91577 eV +One Electron Energy: -303.54712808031508 Eh -8259.93728 eV +Two Electron Energy: 112.34348012206191 Eh 3057.02151 eV + +Virial components: +Potential Energy : -232.15779436564932 Eh -6317.33475 eV +Kinetic Energy : 115.19145317327282 Eh 3134.51880 eV +Virial Ratio : 2.01540815720446 + +DFT components: +N(Alpha) : 12.999999148866 electrons +N(Beta) : 11.999998650263 electrons +N(Total) : 24.999997799129 electrons +E(X) : -14.264975078911 Eh +E(C) : -0.915645498484 Eh +E(XC) : -15.180620577395 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.7066e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.0197e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2319e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.6014e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.2716e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.6056e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754169 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004169 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.3 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966341192377 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000109010 -0.000298063 0.000125323 + 2 C : 0.000004869 0.000119647 -0.000088733 + 3 C : 0.000044591 -0.000273881 0.000268591 + 4 H : 0.000135561 0.000150089 0.000047701 + 5 H : -0.000053790 0.000025146 -0.000121295 + 6 H : -0.000005904 0.000015288 -0.000050062 + 7 H : 0.000012129 0.000070586 0.000045682 + 8 H : -0.000083602 0.000184655 0.000050840 + 9 H : -0.000010345 -0.000012938 -0.000098274 + 10 H : 0.000065499 0.000019472 -0.000179773 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000047648 -0.0000323350 0.0001035405 + +Norm of the Cartesian gradient ... 0.0006706586 +RMS gradient ... 0.0001224450 +MAX gradient ... 0.0002980635 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.647 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.006 sec ( 0.9%) +RI-J Coulomb gradient .... 0.114 sec ( 17.7%) +COSX gradient .... 0.408 sec ( 63.0%) +XC gradient .... 0.119 sec ( 18.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966341192 Eh +Current gradient norm .... 0.000670659 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999581090 +Lowest eigenvalues of augmented Hessian: + -0.000002969 0.000993217 0.007104959 0.014086543 0.133073685 +Length of the computed step .... 0.028954229 +The final length of the internal step .... 0.028954229 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0049656094 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0059334049 RMS(Int)= 0.0049686194 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001486 +Previously predicted energy change .... -0.000003776 +Actually observed energy change .... -0.000005028 +Ratio of predicted to observed change .... 1.331473768 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000050276 0.0000050000 NO + RMS gradient 0.0000933239 0.0001000000 YES + MAX gradient 0.0002605376 0.0003000000 YES + RMS step 0.0049656094 0.0020000000 NO + MAX step 0.0118588589 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.07 + Max(Dihed) 0.68 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5232 0.000062 -0.0000 1.5232 + 2. B(C 2,C 1) 1.5232 0.000069 -0.0000 1.5232 + 3. B(H 3,C 0) 1.1081 0.000043 -0.0001 1.1081 + 4. B(H 4,C 0) 1.1026 0.000007 -0.0000 1.1025 + 5. B(H 5,C 0) 1.1022 0.000036 0.0000 1.1022 + 6. B(H 6,C 1) 1.0997 0.000066 -0.0001 1.0995 + 7. B(H 7,C 2) 1.1081 0.000030 -0.0000 1.1081 + 8. B(H 8,C 2) 1.1023 0.000043 -0.0000 1.1023 + 9. B(H 9,C 2) 1.1026 0.000012 -0.0001 1.1025 + 10. A(H 3,C 0,H 4) 107.31 0.000170 -0.03 107.29 + 11. A(C 1,C 0,H 3) 111.66 -0.000261 0.05 111.70 + 12. A(C 1,C 0,H 5) 110.97 -0.000035 0.02 110.98 + 13. A(H 4,C 0,H 5) 108.39 -0.000037 0.01 108.39 + 14. A(C 1,C 0,H 4) 111.00 0.000086 -0.02 110.98 + 15. A(H 3,C 0,H 5) 107.34 0.000089 -0.02 107.32 + 16. A(C 0,C 1,C 2) 120.89 -0.000056 0.07 120.96 + 17. A(C 2,C 1,H 6) 117.79 0.000015 0.04 117.83 + 18. A(C 0,C 1,H 6) 117.80 0.000029 0.04 117.84 + 19. A(H 7,C 2,H 9) 107.34 0.000204 -0.04 107.30 + 20. A(C 1,C 2,H 9) 110.99 0.000075 -0.02 110.98 + 21. A(H 7,C 2,H 8) 107.35 0.000113 -0.03 107.32 + 22. A(C 1,C 2,H 8) 110.95 -0.000060 0.02 110.97 + 23. A(H 8,C 2,H 9) 108.36 -0.000100 0.03 108.39 + 24. A(C 1,C 2,H 7) 111.68 -0.000222 0.03 111.71 + 25. D(C 2,C 1,C 0,H 4) -42.20 -0.000066 0.67 -41.53 + 26. D(H 6,C 1,C 0,H 3) -80.87 0.000065 0.19 -80.68 + 27. D(C 2,C 1,C 0,H 3) 77.50 0.000032 0.65 78.15 + 28. D(H 6,C 1,C 0,H 4) 159.43 -0.000033 0.21 159.64 + 29. D(C 2,C 1,C 0,H 5) -162.79 -0.000053 0.67 -162.12 + 30. D(H 7,C 2,C 1,H 6) 80.51 -0.000060 -0.17 80.33 + 31. D(H 7,C 2,C 1,C 0) -77.87 -0.000030 -0.64 -78.51 + 32. D(H 9,C 2,C 1,C 0) 41.87 0.000131 -0.68 41.19 + 33. D(H 8,C 2,C 1,H 6) -39.21 -0.000015 -0.17 -39.39 + 34. D(H 8,C 2,C 1,C 0) 162.41 0.000015 -0.64 161.77 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (13.002 %) +Internal coordinates : 0.000 s ( 1.110 %) +B/P matrices and projection : 0.000 s ( 8.113 %) +Hessian update/contruction : 0.000 s ( 6.917 %) +Making the step : 0.000 s ( 6.533 %) +Converting the step to Cartesian: 0.000 s ( 1.345 %) +Storing new data : 0.000 s ( 1.025 %) +Checking convergence : 0.000 s ( 0.406 %) +Final printing : 0.003 s (61.443 %) +Total time : 0.005 s + +Time for energy+gradient : 5.260 s +Time for complete geometry iter : 6.111 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 10 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.332765 -0.020501 0.164771 + C 0.049051 0.473498 -0.243411 + C 1.287701 -0.381464 -0.009159 + H -1.500987 0.087106 1.254697 + H -1.459459 -1.087448 -0.082490 + H -2.123597 0.551490 -0.347375 + H 0.189687 1.556265 -0.373011 + H 1.622402 -0.337656 1.046231 + H 2.128049 -0.038113 -0.634368 + H 1.087551 -1.439468 -0.245981 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.518560 -0.038742 0.311372 + 1 C 6.0000 0 12.011 0.092693 0.894782 -0.459980 + 2 C 6.0000 0 12.011 2.433403 -0.720863 -0.017307 + 3 H 1.0000 0 1.008 -2.836454 0.164607 2.371034 + 4 H 1.0000 0 1.008 -2.757979 -2.054979 -0.155884 + 5 H 1.0000 0 1.008 -4.013017 1.042165 -0.656443 + 6 H 1.0000 0 1.008 0.358457 2.940915 -0.704889 + 7 H 1.0000 0 1.008 3.065896 -0.638077 1.977089 + 8 H 1.0000 0 1.008 4.021429 -0.072024 -1.198782 + 9 H 1.0000 0 1.008 2.055174 -2.720200 -0.464836 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.523175073640 0.00000000 0.00000000 + C 2 1 0 1.523183991924 120.96226545 0.00000000 + H 1 2 3 1.108069242934 111.70472065 78.15242973 + H 1 2 3 1.102526422832 110.97774231 318.47471732 + H 1 2 3 1.102217414936 110.98243349 197.87821642 + H 2 1 3 1.099526508417 117.83980657 201.16276673 + H 3 2 1 1.108057033254 111.71099985 281.49100245 + H 3 2 1 1.102252449363 110.97117894 161.77422667 + H 3 2 1 1.102504575450 110.97616840 41.19024623 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.878383743195 0.00000000 0.00000000 + C 2 1 0 2.878400596310 120.96226545 0.00000000 + H 1 2 3 2.093947406567 111.70472065 78.15242973 + H 1 2 3 2.083472994564 110.97774231 318.47471732 + H 1 2 3 2.082889054268 110.98243349 197.87821642 + H 2 1 3 2.077803977895 117.83980657 201.16276673 + H 3 2 1 2.093924333614 111.71099985 281.49100245 + H 3 2 1 2.082955259739 110.97117894 161.77422667 + H 3 2 1 2.083431708995 110.97616840 41.19024623 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.233582072897 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.207e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40936 +Total number of batches ... 647 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 47 +Average number of points per batch ... 113 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10995 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24065 +Total number of batches ... 195 +Average number of points per batch ... 123 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9662711301396314 0.00e+00 2.36e-04 1.29e-03 3.15e-04 0.2 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662893922658782 -1.83e-05 1.15e-04 7.34e-04 4.10e-04 0.1 + 3 -116.9662918221983432 -2.43e-06 2.36e-05 1.53e-04 7.95e-05 0.1 + 4 -116.9662918983407849 -7.61e-08 3.78e-06 3.46e-05 1.02e-05 0.1 + 5 -116.9662919006144648 -2.27e-09 7.34e-07 3.39e-06 2.27e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.097 sec) +Old exchange energy : -3.614409188 Eh +New exchange energy : -3.614460377 Eh +Exchange energy change after final integration : -0.000051189 Eh +Total energy after final integration : -116.966343090 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96634308950533 Eh -3182.81601 eV + +Components: +Nuclear Repulsion : 74.23358207289701 Eh 2019.99846 eV +Electronic Energy : -191.19987397351147 Eh -5202.81308 eV +One Electron Energy: -303.53946822334467 Eh -8259.72885 eV +Two Electron Energy: 112.33959424983320 Eh 3056.91577 eV + +Virial components: +Potential Energy : -232.15757091854090 Eh -6317.32867 eV +Kinetic Energy : 115.19122782903557 Eh 3134.51266 eV +Virial Ratio : 2.01541016007837 + +DFT components: +N(Alpha) : 12.999999256498 electrons +N(Beta) : 11.999998747651 electrons +N(Total) : 24.999998004148 electrons +E(X) : -14.264996543224 Eh +E(C) : -0.915655702890 Eh +E(XC) : -15.180652246113 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.2737e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.3934e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.3428e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 9.2457e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.2710e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.6991e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754185 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004185 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.4 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966343089505 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000172958 -0.000206001 0.000085320 + 2 C : 0.000029636 0.000210089 -0.000003858 + 3 C : 0.000126438 -0.000224783 0.000115633 + 4 H : 0.000082308 0.000085187 -0.000012107 + 5 H : -0.000024273 0.000029860 -0.000065240 + 6 H : -0.000003863 -0.000013615 -0.000015299 + 7 H : -0.000004807 -0.000000214 0.000008653 + 8 H : -0.000056824 0.000107577 -0.000006213 + 9 H : -0.000007383 -0.000015024 -0.000028685 + 10 H : 0.000031727 0.000026924 -0.000078204 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000025150 -0.0000328335 0.0001087993 + +Norm of the Cartesian gradient ... 0.0004987827 +RMS gradient ... 0.0000910648 +MAX gradient ... 0.0002247830 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.630 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.114 sec ( 18.2%) +COSX gradient .... 0.394 sec ( 62.6%) +XC gradient .... 0.116 sec ( 18.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 34 +Current Energy .... -116.966343090 Eh +Current gradient norm .... 0.000498783 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999969380 +Lowest eigenvalues of augmented Hessian: + -0.000000675 0.001007492 0.006482343 0.014088708 0.123709156 +Length of the computed step .... 0.007825777 +The final length of the internal step .... 0.007825777 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0013421096 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0016646085 RMS(Int)= 0.0013424489 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000338 +Previously predicted energy change .... -0.000001486 +Actually observed energy change .... -0.000001897 +Ratio of predicted to observed change .... 1.277093531 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000018971 0.0000050000 YES + RMS gradient 0.0000600883 0.0001000000 YES + MAX gradient 0.0001562911 0.0003000000 YES + RMS step 0.0013421096 0.0020000000 YES + MAX step 0.0034510565 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0002 Max(Angles) 0.04 + Max(Dihed) 0.20 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5232 0.000136 -0.0002 1.5230 + 2. B(C 2,C 1) 1.5232 0.000139 -0.0002 1.5230 + 3. B(H 3,C 0) 1.1081 -0.000015 0.0000 1.1081 + 4. B(H 4,C 0) 1.1025 -0.000014 0.0000 1.1025 + 5. B(H 5,C 0) 1.1022 0.000004 -0.0000 1.1022 + 6. B(H 6,C 1) 1.0995 -0.000002 -0.0000 1.0995 + 7. B(H 7,C 2) 1.1081 -0.000020 0.0000 1.1081 + 8. B(H 8,C 2) 1.1023 0.000005 -0.0000 1.1022 + 9. B(H 9,C 2) 1.1025 -0.000012 0.0000 1.1025 + 10. A(H 3,C 0,H 4) 107.29 0.000099 -0.04 107.25 + 11. A(C 1,C 0,H 3) 111.70 -0.000156 0.04 111.75 + 12. A(C 1,C 0,H 5) 110.98 0.000008 0.01 110.99 + 13. A(H 4,C 0,H 5) 108.39 -0.000027 0.01 108.40 + 14. A(C 1,C 0,H 4) 110.98 0.000042 -0.01 110.96 + 15. A(H 3,C 0,H 5) 107.32 0.000040 -0.01 107.31 + 16. A(C 0,C 1,C 2) 120.96 -0.000038 0.03 120.99 + 17. A(C 2,C 1,H 6) 117.83 0.000019 0.01 117.84 + 18. A(C 0,C 1,H 6) 117.84 0.000018 0.01 117.85 + 19. A(H 7,C 2,H 9) 107.30 0.000109 -0.04 107.26 + 20. A(C 1,C 2,H 9) 110.98 0.000035 -0.01 110.96 + 21. A(H 7,C 2,H 8) 107.32 0.000051 -0.01 107.30 + 22. A(C 1,C 2,H 8) 110.97 -0.000003 0.01 110.98 + 23. A(H 8,C 2,H 9) 108.39 -0.000049 0.02 108.41 + 24. A(C 1,C 2,H 7) 111.71 -0.000137 0.04 111.75 + 25. D(C 2,C 1,C 0,H 4) -41.53 -0.000022 0.20 -41.33 + 26. D(H 6,C 1,C 0,H 3) -80.68 0.000026 -0.00 -80.69 + 27. D(C 2,C 1,C 0,H 3) 78.15 0.000028 0.17 78.32 + 28. D(H 6,C 1,C 0,H 4) 159.64 -0.000024 0.03 159.66 + 29. D(C 2,C 1,C 0,H 5) -162.12 -0.000021 0.19 -161.93 + 30. D(H 7,C 2,C 1,H 6) 80.33 -0.000025 0.02 80.35 + 31. D(H 7,C 2,C 1,C 0) -78.51 -0.000027 -0.15 -78.66 + 32. D(H 9,C 2,C 1,C 0) 41.19 0.000044 -0.19 41.00 + 33. D(H 8,C 2,C 1,H 6) -39.39 0.000005 0.01 -39.38 + 34. D(H 8,C 2,C 1,C 0) 161.77 0.000003 -0.17 161.61 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (23.103 %) +Internal coordinates : 0.000 s ( 1.716 %) +B/P matrices and projection : 0.000 s (14.030 %) +Hessian update/contruction : 0.000 s (13.115 %) +Making the step : 0.000 s (10.484 %) +Converting the step to Cartesian: 0.000 s ( 2.059 %) +Storing new data : 0.000 s ( 2.173 %) +Checking convergence : 0.000 s ( 0.724 %) +Final printing : 0.001 s (32.482 %) +Total time : 0.003 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 10 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.332765 -0.020314 0.164762 + C 0.049224 0.473976 -0.241813 + C 1.287744 -0.381321 -0.009299 + H -1.503201 0.087467 1.254341 + H -1.458260 -1.087593 -0.081757 + H -2.123240 0.550757 -0.348950 + H 0.189824 1.556664 -0.371872 + H 1.624397 -0.338103 1.045523 + H 2.127413 -0.038519 -0.635704 + H 1.086496 -1.439306 -0.245326 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.518561 -0.038389 0.311355 + 1 C 6.0000 0 12.011 0.093020 0.895685 -0.456961 + 2 C 6.0000 0 12.011 2.433484 -0.720592 -0.017573 + 3 H 1.0000 0 1.008 -2.840638 0.165289 2.370361 + 4 H 1.0000 0 1.008 -2.755711 -2.055253 -0.154499 + 5 H 1.0000 0 1.008 -4.012343 1.040780 -0.659419 + 6 H 1.0000 0 1.008 0.358716 2.941668 -0.702737 + 7 H 1.0000 0 1.008 3.069666 -0.638921 1.975752 + 8 H 1.0000 0 1.008 4.020228 -0.072791 -1.201306 + 9 H 1.0000 0 1.008 2.053179 -2.719893 -0.463599 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522997342155 0.00000000 0.00000000 + C 2 1 0 1.522999954981 120.99071255 0.00000000 + H 1 2 3 1.108083006319 111.74653922 78.32084331 + H 1 2 3 1.102544178689 110.96301445 318.67237627 + H 1 2 3 1.102213008399 110.98938103 198.06907628 + H 2 1 3 1.099498008971 117.85297713 200.99224342 + H 3 2 1 1.108085204288 111.74599584 281.33860343 + H 3 2 1 1.102242766412 110.98183338 161.60894526 + H 3 2 1 1.102515803384 110.96397729 41.00004605 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.878047879363 0.00000000 0.00000000 + C 2 1 0 2.878052816889 120.99071255 0.00000000 + H 1 2 3 2.093973415595 111.74653922 78.32084331 + H 1 2 3 2.083506548271 110.96301445 318.67237627 + H 1 2 3 2.082880727120 110.98938103 198.06907628 + H 2 1 3 2.077750121747 117.85297713 200.99224342 + H 3 2 1 2.093977569155 111.74599584 281.33860343 + H 3 2 1 2.082936961614 110.98183338 161.60894526 + H 3 2 1 2.083452926716 110.96397729 41.00004605 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 6s3p contracted to 2s1p pattern {33/3} + Group 2 Type H : 3s contracted to 1s pattern {3} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} + Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1102 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.236144498171 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.207e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40936 +Total number of batches ... 646 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5315 +Total number of batches ... 47 +Average number of points per batch ... 113 +Average number of grid points per atom ... 532 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10996 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1100 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24065 +Total number of batches ... 195 +Average number of points per batch ... 123 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input_reactant + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 74.2361444982 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input_reactant.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9662904921719786 0.00e+00 6.93e-05 4.58e-04 9.15e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9662920212992532 -1.53e-06 3.24e-05 2.63e-04 1.15e-04 0.1 + 3 -116.9662922091887793 -1.88e-07 5.78e-06 5.37e-05 2.06e-05 0.1 + 4 -116.9662922145369777 -5.35e-09 1.10e-06 1.29e-05 3.60e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.094 sec) +Old exchange energy : -3.614421616 Eh +New exchange energy : -3.614472891 Eh +Exchange energy change after final integration : -0.000051275 Eh +Total energy after final integration : -116.966343489 Eh + **** ENERGY FILE WAS UPDATED (input_reactant.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.96634348920396 Eh -3182.81602 eV + +Components: +Nuclear Repulsion : 74.23614449817147 Eh 2020.06819 eV +Electronic Energy : -191.20243671270845 Eh -5202.88281 eV +One Electron Energy: -303.54431519643606 Eh -8259.86074 eV +Two Electron Energy: 112.34187848372761 Eh 3056.97793 eV + +Virial components: +Potential Energy : -232.15765852586961 Eh -6317.33106 eV +Kinetic Energy : 115.19131503666564 Eh 3134.51504 eV +Virial Ratio : 2.01540939481395 + +DFT components: +N(Alpha) : 12.999999255707 electrons +N(Beta) : 11.999998753472 electrons +N(Total) : 24.999998009179 electrons +E(X) : -14.265048399762 Eh +E(C) : -0.915666580723 Eh +E(XC) : -15.180714980485 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 5.3482e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2863e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0995e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.6943e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 3.6014e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.2156e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754190 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004190 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.001573 -272.1566 + 1 1.0000 -10.001561 -272.1563 + 2 1.0000 -9.971246 -271.3314 + 3 1.0000 -0.726490 -19.7688 + 4 1.0000 -0.645922 -17.5764 + 5 1.0000 -0.527567 -14.3558 + 6 1.0000 -0.404286 -11.0012 + 7 1.0000 -0.384521 -10.4634 + 8 1.0000 -0.361971 -9.8497 + 9 1.0000 -0.347930 -9.4677 + 10 1.0000 -0.303175 -8.2498 + 11 1.0000 -0.301495 -8.2041 + 12 1.0000 -0.118680 -3.2294 + 13 0.0000 0.381916 10.3925 + 14 0.0000 0.396568 10.7912 + 15 0.0000 0.427798 11.6410 + 16 0.0000 0.444554 12.0969 + 17 0.0000 0.465735 12.6733 + 18 0.0000 0.474064 12.8999 + 19 0.0000 0.492527 13.4023 + 20 0.0000 0.533556 14.5188 + 21 0.0000 0.568294 15.4641 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.002656 -272.1861 + 1 1.0000 -10.002642 -272.1857 + 2 1.0000 -9.955865 -270.9129 + 3 1.0000 -0.708308 -19.2740 + 4 1.0000 -0.644482 -17.5372 + 5 1.0000 -0.502878 -13.6840 + 6 1.0000 -0.398490 -10.8435 + 7 1.0000 -0.369328 -10.0499 + 8 1.0000 -0.357774 -9.7355 + 9 1.0000 -0.343666 -9.3516 + 10 1.0000 -0.296845 -8.0776 + 11 1.0000 -0.295852 -8.0505 + 12 0.0000 0.080578 2.1927 + 13 0.0000 0.388787 10.5794 + 14 0.0000 0.425915 11.5897 + 15 0.0000 0.433401 11.7934 + 16 0.0000 0.449425 12.2295 + 17 0.0000 0.473332 12.8800 + 18 0.0000 0.483977 13.1697 + 19 0.0000 0.494892 13.4667 + 20 0.0000 0.546816 14.8796 + 21 0.0000 0.581917 15.8348 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 C : -0.230384 -0.072340 + 1 C : -0.047432 1.042792 + 2 C : -0.230407 -0.072335 + 3 H : 0.074747 0.049008 + 4 H : 0.074909 0.012683 + 5 H : 0.076122 0.011380 + 6 H : 0.056667 -0.044241 + 7 H : 0.074756 0.048998 + 8 H : 0.076104 0.011571 + 9 H : 0.074918 0.012484 +Sum of atomic charges : -0.0000000 +Sum of atomic spin populations: 1.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 C s : 3.193097 s : 3.193097 + pz : 1.021044 p : 3.037287 + px : 0.990223 + py : 1.026021 + + 1 C s : 3.201487 s : 3.201487 + pz : 0.997549 p : 2.845945 + px : 0.896220 + py : 0.952177 + + 2 C s : 3.193089 s : 3.193089 + pz : 1.023854 p : 3.037318 + px : 0.997942 + py : 1.015522 + + 3 H s : 0.925253 s : 0.925253 + + 4 H s : 0.925091 s : 0.925091 + + 5 H s : 0.923878 s : 0.923878 + + 6 H s : 0.943333 s : 0.943333 + + 7 H s : 0.925244 s : 0.925244 + + 8 H s : 0.923896 s : 0.923896 + + 9 H s : 0.925082 s : 0.925082 + + +SPIN + 0 C s : -0.015023 s : -0.015023 + pz : -0.019901 p : -0.057317 + px : -0.028536 + py : -0.008880 + + 1 C s : 0.082569 s : 0.082569 + pz : 0.848300 p : 0.960223 + px : 0.039231 + py : 0.072691 + + 2 C s : -0.015022 s : -0.015022 + pz : -0.018342 p : -0.057313 + px : -0.024372 + py : -0.014600 + + 3 H s : 0.049008 s : 0.049008 + + 4 H s : 0.012683 s : 0.012683 + + 5 H s : 0.011380 s : 0.011380 + + 6 H s : -0.044241 s : -0.044241 + + 7 H s : 0.048998 s : 0.048998 + + 8 H s : 0.011571 s : 0.011571 + + 9 H s : 0.012484 s : 0.012484 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 C : -0.125933 -0.054485 + 1 C : -0.024274 1.006697 + 2 C : -0.125957 -0.054481 + 3 H : 0.041819 0.045238 + 4 H : 0.041526 0.011616 + 5 H : 0.042469 0.010389 + 6 H : 0.024533 -0.032201 + 7 H : 0.041826 0.045229 + 8 H : 0.042461 0.010569 + 9 H : 0.041530 0.011429 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 C s : 3.013497 s : 3.013497 + pz : 1.041378 p : 3.112436 + px : 1.022927 + py : 1.048132 + + 1 C s : 3.089943 s : 3.089943 + pz : 1.005455 p : 2.934331 + px : 0.945064 + py : 0.983811 + + 2 C s : 3.013494 s : 3.013494 + pz : 1.043495 p : 3.112464 + px : 1.028191 + py : 1.040778 + + 3 H s : 0.958181 s : 0.958181 + + 4 H s : 0.958474 s : 0.958474 + + 5 H s : 0.957531 s : 0.957531 + + 6 H s : 0.975467 s : 0.975467 + + 7 H s : 0.958174 s : 0.958174 + + 8 H s : 0.957539 s : 0.957539 + + 9 H s : 0.958470 s : 0.958470 + + +SPIN + 0 C s : -0.009097 s : -0.009097 + pz : -0.015272 p : -0.045388 + px : -0.023006 + py : -0.007111 + + 1 C s : 0.061483 s : 0.061483 + pz : 0.845962 p : 0.945213 + px : 0.033216 + py : 0.066035 + + 2 C s : -0.009096 s : -0.009096 + pz : -0.014083 p : -0.045385 + px : -0.019549 + py : -0.011753 + + 3 H s : 0.045238 s : 0.045238 + + 4 H s : 0.011616 s : 0.011616 + + 5 H s : 0.010389 s : 0.010389 + + 6 H s : -0.032201 s : -0.032201 + + 7 H s : 0.045229 s : 0.045229 + + 8 H s : 0.010569 s : 0.010569 + + 9 H s : 0.011429 s : 0.011429 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 C 6.2304 6.0000 -0.2304 3.9600 3.9579 0.0021 + 1 C 6.0474 6.0000 -0.0474 3.9410 3.1031 0.8379 + 2 C 6.2304 6.0000 -0.2304 3.9601 3.9579 0.0021 + 3 H 0.9253 1.0000 0.0747 0.9944 0.9920 0.0024 + 4 H 0.9251 1.0000 0.0749 0.9944 0.9942 0.0002 + 5 H 0.9239 1.0000 0.0761 0.9942 0.9941 0.0001 + 6 H 0.9433 1.0000 0.0567 0.9968 0.9948 0.0020 + 7 H 0.9252 1.0000 0.0748 0.9944 0.9920 0.0024 + 8 H 0.9239 1.0000 0.0761 0.9942 0.9941 0.0001 + 9 H 0.9251 1.0000 0.0749 0.9944 0.9942 0.0002 + + Mayer bond orders larger than 0.100000 +B( 0-C , 1-C ) : 1.0265 B( 0-C , 3-H ) : 0.9580 B( 0-C , 4-H ) : 0.9735 +B( 0-C , 5-H ) : 0.9744 B( 1-C , 2-C ) : 1.0265 B( 1-C , 6-H ) : 0.9637 +B( 2-C , 7-H ) : 0.9580 B( 2-C , 8-H ) : 0.9743 B( 2-C , 9-H ) : 0.9736 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.787 sec +Sum of individual times .... 0.764 sec ( 97.1%) + +SCF preparation .... 0.216 sec ( 27.4%) +Fock matrix formation .... 0.479 sec ( 60.9%) + Startup .... 0.006 sec ( 1.3% of F) + Split-RI-J .... 0.025 sec ( 5.3% of F) + Chain of spheres X .... 0.308 sec ( 64.3% of F) + XC integration .... 0.126 sec ( 26.2% of F) + Basis function eval. .... 0.032 sec ( 25.5% of XC) + Density eval. .... 0.010 sec ( 7.7% of XC) + XC-Functional eval. .... 0.029 sec ( 23.4% of XC) + XC-Potential eval. .... 0.008 sec ( 6.0% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.006 sec ( 0.8%) +Total Energy calculation .... 0.007 sec ( 0.9%) +Population analysis .... 0.024 sec ( 3.0%) +Orbital Transformation .... 0.006 sec ( 0.7%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.007 sec ( 0.9%) +SOSCF solution .... 0.020 sec ( 2.5%) +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.4 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.966343489204 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + +--------------------------------------------------------------- + PRODUCT OPTIMIZATION +--------------------------------------------------------------- + +Geometry optimization settings: +Update method Update .... BFGS +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Almloef's Model +Max. no of cycles MaxIter .... 50 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Evaluating the initial hessian ... (Almloef) done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 11 +The number of degrees of freedom .... 24 + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value Approx d2E/dq + ----------------------------------------------------------------- + 1. B(C 1,C 0) 1.4907 0.431535 + 2. B(C 2,C 1) 1.5196 0.388186 + 3. B(H 3,C 1) 1.0953 0.353131 + 4. B(H 4,C 0) 1.0842 0.367844 + 5. B(H 5,C 0) 1.0843 0.367743 + 6. B(H 6,C 1) 1.0950 0.353519 + 7. B(H 7,C 2) 1.0953 0.353139 + 8. B(H 8,C 2) 1.0947 0.353907 + 9. B(H 9,C 2) 1.0953 0.353128 + 10. A(H 4,C 0,H 5) 118.4265 0.292780 + 11. A(C 1,C 0,H 4) 119.7065 0.333301 + 12. A(C 1,C 0,H 5) 120.7384 0.333286 + 13. A(C 0,C 1,H 3) 109.0825 0.331054 + 14. A(C 2,C 1,H 3) 109.3307 0.325324 + 15. A(C 0,C 1,C 2) 111.9970 0.374928 + 16. A(H 3,C 1,H 6) 107.5252 0.289111 + 17. A(C 2,C 1,H 6) 109.7197 0.325382 + 18. A(C 0,C 1,H 6) 109.0787 0.331115 + 19. A(H 7,C 2,H 9) 108.1195 0.289062 + 20. A(C 1,C 2,H 9) 111.2352 0.325323 + 21. A(H 7,C 2,H 8) 108.0047 0.289162 + 22. A(C 1,C 2,H 8) 110.2088 0.325441 + 23. A(H 8,C 2,H 9) 107.9504 0.289161 + 24. A(C 1,C 2,H 7) 111.1968 0.325325 + 25. D(C 2,C 1,C 0,H 5) -38.3953 0.013751 + 26. D(H 3,C 1,C 0,H 5) -159.5610 0.013751 + 27. D(C 2,C 1,C 0,H 4) 153.9381 0.013751 + 28. D(H 6,C 1,C 0,H 4) -84.4085 0.013751 + 29. D(H 3,C 1,C 0,H 4) 32.7724 0.013751 + 30. D(H 7,C 2,C 1,H 3) 61.3595 0.011985 + 31. D(H 7,C 2,C 1,C 0) -59.6629 0.011985 + 32. D(H 8,C 2,C 1,H 3) -58.3781 0.011985 + 33. D(H 8,C 2,C 1,C 0) -179.4004 0.011985 + 34. D(H 8,C 2,C 1,H 6) 59.3151 0.011985 + 35. D(H 7,C 2,C 1,H 6) 179.0526 0.011985 + ----------------------------------------------------------------- + +Number of atoms .... 10 +Number of degrees of freedom .... 35 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.158612 0.295376 0.513393 + C 0.182423 -0.311088 -0.436112 + C -1.253870 0.010906 -0.058710 + H 0.319912 -1.397702 -0.445636 + H 2.133913 -0.159615 0.644843 + H 0.991323 1.285155 0.923296 + H 0.390236 0.056441 -1.446462 + H -1.493120 -0.361585 0.943149 + H -1.944973 -0.456491 -0.767465 + H -1.435157 1.091028 -0.072835 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.189460 0.558179 0.970171 + 1 C 6.0000 0 12.011 0.344730 -0.587871 -0.824133 + 2 C 6.0000 0 12.011 -2.369471 0.020609 -0.110946 + 3 H 1.0000 0 1.008 0.604545 -2.641275 -0.842130 + 4 H 1.0000 0 1.008 4.032511 -0.301629 1.218577 + 5 H 1.0000 0 1.008 1.873329 2.428591 1.744776 + 6 H 1.0000 0 1.008 0.737439 0.106658 -2.733418 + 7 H 1.0000 0 1.008 -2.821589 -0.683296 1.782293 + 8 H 1.0000 0 1.008 -3.675466 -0.862643 -1.450299 + 9 H 1.0000 0 1.008 -2.712054 2.061745 -0.137639 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.487425914027 0.00000000 0.00000000 + C 2 1 0 1.487425980527 119.77399045 0.00000000 + H 1 2 3 1.093645997827 110.41802604 74.50386961 + H 1 2 3 1.093852738124 111.00517693 313.49755566 + H 1 2 3 1.094044400362 110.01195059 194.03594548 + H 2 1 3 1.084716628382 119.23299408 195.22108514 + H 3 2 1 1.093646008193 110.41801850 285.49610873 + H 3 2 1 1.094044350795 110.01194450 165.96404977 + H 3 2 1 1.093852602978 111.00522169 46.50237252 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.810827622008 0.00000000 0.00000000 + C 2 1 0 2.810827747675 119.77399045 0.00000000 + H 1 2 3 2.066691423352 110.41802604 74.50386961 + H 1 2 3 2.067082105895 111.00517693 313.49755566 + H 1 2 3 2.067444295035 110.01195059 194.03594548 + H 2 1 3 2.049817360552 119.23299408 195.22108514 + H 3 2 1 2.066691442941 110.41801850 285.49610873 + H 3 2 1 2.067444201366 110.01194450 165.96404977 + H 3 2 1 2.067081850506 111.00522169 46.50237252 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 6s3p contracted to 2s1p pattern {33/3} + Group 2 Type H : 3s contracted to 1s pattern {3} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} + Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1109 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 76.133400937485 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.037e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40903 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4090 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5298 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10965 +Total number of batches ... 90 +Average number of points per batch ... 121 +Average number of grid points per atom ... 1096 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24067 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2407 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input_product + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 76.1334009375 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 50 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +------------------------------ +INITIAL GUESS: MODEL POTENTIAL +------------------------------ +Loading Hartree-Fock densities ... done +Calculating cut-offs ... done +Initializing the effective Hamiltonian ... done +Setting up the integral package (SHARK) ... done +Starting the Coulomb interaction ... done ( 0.0 sec) +Making the grid ... done ( 0.0 sec) +Mapping shells ... done +Starting the XC term evaluation ... done ( 0.0 sec) + promolecular density results + # of electrons = 24.996761377 + EX = -17.457880141 + EC = -0.773497767 + EX+EC = -18.231377908 +Transforming the Hamiltonian ... done ( 0.0 sec) +Diagonalizing the Hamiltonian ... done ( 0.0 sec) +Back transforming the eigenvectors ... done ( 0.0 sec) +Now organizing SCF variables ... done + ------------------ + INITIAL GUESS DONE ( 0.1 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 6.0 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +Warning: Unable to find asked property in file 'input_product.property.txt' + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.9128104040608349 0.00e+00 5.74e-03 2.68e-02 4.30e-02 0.700 0.1 + 2 -116.9302810763153246 -1.75e-02 4.35e-03 2.18e-02 2.51e-02 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -116.9392690883551182 -8.99e-03 1.80e-03 1.31e-02 1.34e-02 0.700 0.1 + 4 -116.9444763936652549 -5.21e-03 3.42e-03 2.89e-02 8.83e-03 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -116.9553680063703354 -1.09e-02 4.89e-04 5.05e-03 2.03e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -116.9554048695225248 -3.69e-05 2.61e-04 2.06e-03 6.69e-04 0.1 + 7 -116.9554141370313829 -9.27e-06 1.78e-04 1.35e-03 4.18e-04 0.1 + 8 -116.9554159811355731 -1.84e-06 3.68e-05 2.05e-04 1.25e-04 0.1 + 9 -116.9554161719376708 -1.91e-07 5.89e-06 4.04e-05 1.16e-05 0.1 + 10 -116.9554161746233802 -2.69e-09 2.14e-06 1.50e-05 7.72e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 10 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.097 sec) +Old exchange energy : -3.623532883 Eh +New exchange energy : -3.623546298 Eh +Exchange energy change after final integration : -0.000013415 Eh +Total energy after final integration : -116.955429589 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95542958917348 Eh -3182.51904 eV + +Components: +Nuclear Repulsion : 76.13340093748509 Eh 2071.69516 eV +Electronic Energy : -193.08881711210847 Eh -5254.21383 eV +One Electron Energy: -307.21410845598189 Eh -8359.72089 eV +Two Electron Energy: 114.12529134387341 Eh 3105.50706 eV + +Virial components: +Potential Energy : -232.28361465562386 Eh -6320.75850 eV +Kinetic Energy : 115.32818506645040 Eh 3138.23946 eV +Virial Ratio : 2.01410968638573 + +DFT components: +N(Alpha) : 13.000012338048 electrons +N(Beta) : 12.000011922889 electrons +N(Total) : 25.000024260937 electrons +E(X) : -14.294019684240 Eh +E(C) : -0.918021809884 Eh +E(XC) : -15.212041494125 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.6857e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4955e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.1434e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.0255e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.7163e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.2965e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754163 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004163 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.012426 -272.4520 + 1 1.0000 -9.999721 -272.1063 + 2 1.0000 -9.961538 -271.0672 + 3 1.0000 -0.743835 -20.2408 + 4 1.0000 -0.633409 -17.2359 + 5 1.0000 -0.543455 -14.7882 + 6 1.0000 -0.421722 -11.4756 + 7 1.0000 -0.400732 -10.9045 + 8 1.0000 -0.366262 -9.9665 + 9 1.0000 -0.323373 -8.7994 + 10 1.0000 -0.304511 -8.2862 + 11 1.0000 -0.299496 -8.1497 + 12 1.0000 -0.131548 -3.5796 + 13 0.0000 0.386882 10.5276 + 14 0.0000 0.397667 10.8211 + 15 0.0000 0.426447 11.6042 + 16 0.0000 0.453795 12.3484 + 17 0.0000 0.479303 13.0425 + 18 0.0000 0.515633 14.0311 + 19 0.0000 0.520339 14.1591 + 20 0.0000 0.535150 14.5622 + 21 0.0000 0.580959 15.8087 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.013553 -272.4826 + 1 1.0000 -9.999357 -272.0963 + 2 1.0000 -9.945835 -270.6399 + 3 1.0000 -0.734878 -19.9970 + 4 1.0000 -0.613754 -16.7011 + 5 1.0000 -0.525830 -14.3086 + 6 1.0000 -0.416171 -11.3246 + 7 1.0000 -0.394505 -10.7350 + 8 1.0000 -0.360392 -9.8068 + 9 1.0000 -0.316869 -8.6224 + 10 1.0000 -0.299178 -8.1410 + 11 1.0000 -0.294598 -8.0164 + 12 0.0000 0.079613 2.1664 + 13 0.0000 0.392812 10.6890 + 14 0.0000 0.412080 11.2133 + 15 0.0000 0.431986 11.7549 + 16 0.0000 0.473934 12.8964 + 17 0.0000 0.482232 13.1222 + 18 0.0000 0.520527 14.1643 + 19 0.0000 0.523007 14.2317 + 20 0.0000 0.548765 14.9327 + 21 0.0000 0.593288 16.1442 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 C : -0.134081 1.091118 + 1 C : -0.147908 -0.074480 + 2 C : -0.218791 0.016911 + 3 H : 0.077172 0.012791 + 4 H : 0.062073 -0.047481 + 5 H : 0.062286 -0.047397 + 6 H : 0.077860 0.050944 + 7 H : 0.074912 -0.001126 + 8 H : 0.073207 -0.000298 + 9 H : 0.073269 -0.000983 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 1.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 C s : 3.199555 s : 3.199555 + pz : 0.982616 p : 2.934527 + px : 0.968291 + py : 0.983620 + + 1 C s : 3.169037 s : 3.169037 + pz : 1.001359 p : 2.978872 + px : 0.959465 + py : 1.018048 + + 2 C s : 3.185648 s : 3.185648 + pz : 1.030086 p : 3.033143 + px : 0.972161 + py : 1.030896 + + 3 H s : 0.922828 s : 0.922828 + + 4 H s : 0.937927 s : 0.937927 + + 5 H s : 0.937714 s : 0.937714 + + 6 H s : 0.922140 s : 0.922140 + + 7 H s : 0.925088 s : 0.925088 + + 8 H s : 0.926793 s : 0.926793 + + 9 H s : 0.926731 s : 0.926731 + + +SPIN + 0 C s : 0.078002 s : 0.078002 + pz : 0.610425 p : 1.013116 + px : 0.173108 + py : 0.229584 + + 1 C s : -0.015626 s : -0.015626 + pz : -0.027139 p : -0.058854 + px : -0.018653 + py : -0.013062 + + 2 C s : 0.003942 s : 0.003942 + pz : 0.001139 p : 0.012969 + px : 0.009870 + py : 0.001960 + + 3 H s : 0.012791 s : 0.012791 + + 4 H s : -0.047481 s : -0.047481 + + 5 H s : -0.047397 s : -0.047397 + + 6 H s : 0.050944 s : 0.050944 + + 7 H s : -0.001126 s : -0.001126 + + 8 H s : -0.000298 s : -0.000298 + + 9 H s : -0.000983 s : -0.000983 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 C : -0.079672 1.050445 + 1 C : -0.065182 -0.054751 + 2 C : -0.118291 0.015740 + 3 H : 0.041086 0.011665 + 4 H : 0.030539 -0.034106 + 5 H : 0.030833 -0.034029 + 6 H : 0.041981 0.047146 + 7 H : 0.040401 -0.000985 + 8 H : 0.039111 -0.000357 + 9 H : 0.039193 -0.000769 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 C s : 3.070288 s : 3.070288 + pz : 1.002091 p : 3.009385 + px : 0.999118 + py : 1.008176 + + 1 C s : 3.000958 s : 3.000958 + pz : 1.026197 p : 3.064223 + px : 0.998704 + py : 1.039323 + + 2 C s : 3.006387 s : 3.006387 + pz : 1.051610 p : 3.111904 + px : 1.008026 + py : 1.052268 + + 3 H s : 0.958914 s : 0.958914 + + 4 H s : 0.969461 s : 0.969461 + + 5 H s : 0.969167 s : 0.969167 + + 6 H s : 0.958019 s : 0.958019 + + 7 H s : 0.959599 s : 0.959599 + + 8 H s : 0.960889 s : 0.960889 + + 9 H s : 0.960807 s : 0.960807 + + +SPIN + 0 C s : 0.053611 s : 0.053611 + pz : 0.606892 p : 0.996834 + px : 0.166630 + py : 0.223312 + + 1 C s : -0.009139 s : -0.009139 + pz : -0.020793 p : -0.045612 + px : -0.014653 + py : -0.010166 + + 2 C s : 0.003575 s : 0.003575 + pz : 0.000968 p : 0.012165 + px : 0.009497 + py : 0.001700 + + 3 H s : 0.011665 s : 0.011665 + + 4 H s : -0.034106 s : -0.034106 + + 5 H s : -0.034029 s : -0.034029 + + 6 H s : 0.047146 s : 0.047146 + + 7 H s : -0.000985 s : -0.000985 + + 8 H s : -0.000357 s : -0.000357 + + 9 H s : -0.000769 s : -0.000769 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 C 6.1341 6.0000 -0.1341 3.9531 3.0413 0.9118 + 1 C 6.1479 6.0000 -0.1479 3.9672 3.9648 0.0023 + 2 C 6.2188 6.0000 -0.2188 3.9607 3.9604 0.0002 + 3 H 0.9228 1.0000 0.0772 0.9940 0.9939 0.0002 + 4 H 0.9379 1.0000 0.0621 0.9961 0.9939 0.0023 + 5 H 0.9377 1.0000 0.0623 0.9961 0.9939 0.0022 + 6 H 0.9221 1.0000 0.0779 0.9939 0.9913 0.0026 + 7 H 0.9251 1.0000 0.0749 0.9944 0.9944 0.0000 + 8 H 0.9268 1.0000 0.0732 0.9946 0.9946 0.0000 + 9 H 0.9267 1.0000 0.0733 0.9946 0.9946 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-C , 1-C ) : 1.0356 B( 0-C , 4-H ) : 0.9728 B( 0-C , 5-H ) : 0.9717 +B( 1-C , 2-C ) : 1.0009 B( 1-C , 3-H ) : 0.9637 B( 1-C , 6-H ) : 0.9466 +B( 2-C , 7-H ) : 0.9788 B( 2-C , 8-H ) : 0.9783 B( 2-C , 9-H ) : 0.9784 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 1 sec + +Total time .... 1.345 sec +Sum of individual times .... 1.320 sec ( 98.1%) + +SCF preparation .... 0.220 sec ( 16.4%) +Fock matrix formation .... 0.975 sec ( 72.4%) + Startup .... 0.011 sec ( 1.1% of F) + Split-RI-J .... 0.062 sec ( 6.3% of F) + Chain of spheres X .... 0.578 sec ( 59.3% of F) + XC integration .... 0.287 sec ( 29.5% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.083 sec ( 28.7% of XC) + Density eval. .... 0.024 sec ( 8.5% of XC) + XC-Functional eval. .... 0.072 sec ( 25.2% of XC) + XC-Potential eval. .... 0.022 sec ( 7.6% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.015 sec ( 1.1%) +Total Energy calculation .... 0.016 sec ( 1.2%) +Population analysis .... 0.010 sec ( 0.7%) +Orbital Transformation .... 0.011 sec ( 0.9%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.046 sec ( 3.5%) +SOSCF solution .... 0.027 sec ( 2.0%) +Finished LeanSCF after 1.4 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.5 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.955429589173 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.010486869 -0.001796698 -0.010417670 + 2 C : -0.008618107 0.006314662 0.001391540 + 3 C : 0.022647966 -0.003348387 -0.001016439 + 4 H : -0.001381915 0.007606470 0.003263394 + 5 H : -0.008944861 0.002117009 -0.002079320 + 6 H : 0.001054129 -0.008304732 -0.003101729 + 7 H : 0.000466033 -0.001164705 0.013352308 + 8 H : 0.000386297 0.001351924 -0.003909247 + 9 H : 0.004588942 0.001659859 0.002797334 + 10 H : 0.000288385 -0.004435403 -0.000280171 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000206698 0.0000266508 0.0000002719 + +Norm of the Cartesian gradient ... 0.0367493251 +RMS gradient ... 0.0067094781 +MAX gradient ... 0.0226479659 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.666 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.115 sec ( 17.3%) +COSX gradient .... 0.422 sec ( 63.4%) +XC gradient .... 0.123 sec ( 18.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 35 +Current Energy .... -116.955429589 Eh +Current gradient norm .... 0.036749325 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Evaluating the initial hessian .... (Almloef) done +Projecting the Hessian .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.992627045 +Lowest eigenvalues of augmented Hessian: + -0.005107785 0.011987902 0.013751385 0.016597567 0.104540845 +Length of the computed step .... 0.122109007 +The final length of the internal step .... 0.122109007 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0206401893 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0387587996 RMS(Int)= 0.0206194660 +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0074745530 0.0001000000 NO + MAX gradient 0.0279923347 0.0003000000 NO + RMS step 0.0206401893 0.0020000000 NO + MAX step 0.0711740957 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0377 Max(Angles) 1.06 + Max(Dihed) 1.27 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.4907 -0.025217 0.0306 1.5213 + 2. B(C 2,C 1) 1.5196 -0.027992 0.0377 1.5572 + 3. B(H 3,C 1) 1.0953 -0.007747 0.0114 1.1068 + 4. B(H 4,C 0) 1.0842 -0.009187 0.0130 1.0972 + 5. B(H 5,C 0) 1.0843 -0.008916 0.0127 1.0969 + 6. B(H 6,C 1) 1.0950 -0.012623 0.0186 1.1136 + 7. B(H 7,C 2) 1.0953 -0.004121 0.0061 1.1014 + 8. B(H 8,C 2) 1.0947 -0.005416 0.0080 1.1027 + 9. B(H 9,C 2) 1.0953 -0.004418 0.0065 1.1018 + 10. A(H 4,C 0,H 5) 118.43 0.001508 -0.35 118.08 + 11. A(C 1,C 0,H 4) 119.71 -0.002693 0.41 120.11 + 12. A(C 1,C 0,H 5) 120.74 0.001218 -0.26 120.48 + 13. A(C 0,C 1,H 3) 109.08 0.000632 0.18 109.26 + 14. A(C 2,C 1,H 3) 109.33 0.000350 0.03 109.36 + 15. A(C 0,C 1,C 2) 112.00 -0.004156 0.96 112.96 + 16. A(H 3,C 1,H 6) 107.53 0.001684 -1.06 106.46 + 17. A(C 2,C 1,H 6) 109.72 0.003703 -0.79 108.93 + 18. A(C 0,C 1,H 6) 109.08 -0.001997 0.60 109.68 + 19. A(H 7,C 2,H 9) 108.12 0.000656 -0.17 107.95 + 20. A(C 1,C 2,H 9) 111.24 0.000831 -0.18 111.05 + 21. A(H 7,C 2,H 8) 108.00 0.000481 -0.00 108.00 + 22. A(C 1,C 2,H 8) 110.21 -0.003108 0.56 110.77 + 23. A(H 8,C 2,H 9) 107.95 -0.000437 0.04 107.99 + 24. A(C 1,C 2,H 7) 111.20 0.001579 -0.25 110.94 + 25. D(C 2,C 1,C 0,H 5) -38.40 -0.000668 -0.27 -38.66 + 26. D(H 3,C 1,C 0,H 5) -159.56 0.001157 -1.05 -160.61 + 27. D(C 2,C 1,C 0,H 4) 153.94 -0.001021 0.86 154.79 + 28. D(H 6,C 1,C 0,H 4) -84.41 -0.000444 0.91 -83.50 + 29. D(H 3,C 1,C 0,H 4) 32.77 0.000804 0.08 32.85 + 30. D(H 7,C 2,C 1,H 3) 61.36 -0.002146 0.66 62.02 + 31. D(H 7,C 2,C 1,C 0) -59.66 -0.000471 -0.21 -59.87 + 32. D(H 8,C 2,C 1,H 3) -58.38 -0.001726 0.45 -57.92 + 33. D(H 8,C 2,C 1,C 0) -179.40 -0.000051 -0.41 -179.82 + 34. D(H 8,C 2,C 1,H 6) 59.32 0.002685 -1.27 58.04 + 35. D(H 7,C 2,C 1,H 6) 179.05 0.002265 -1.07 177.98 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (12.836 %) +Internal coordinates : 0.000 s ( 2.578 %) +B/P matrices and projection : 0.000 s (22.180 %) +Hessian update/contruction : 0.000 s (11.439 %) +Making the step : 0.000 s (15.467 %) +Converting the step to Cartesian: 0.000 s ( 2.954 %) +Storing new data : 0.000 s ( 2.417 %) +Checking convergence : 0.000 s ( 0.107 %) +Final printing : 0.001 s (29.807 %) +Total time : 0.002 s + +Time for energy+gradient : 5.961 s +Time for complete geometry iter : 6.805 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.193247 0.299629 0.530204 + C 0.189908 -0.315851 -0.433564 + C -1.287002 0.009610 -0.062421 + H 0.329591 -1.413573 -0.454070 + H 2.185152 -0.152532 0.655183 + H 1.029149 1.304924 0.937295 + H 0.391072 0.047181 -1.466981 + H -1.532787 -0.368036 0.942594 + H -1.982354 -0.455611 -0.780763 + H -1.466677 1.096683 -0.070016 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.254911 0.566217 1.001940 + 1 C 6.0000 0 12.011 0.358874 -0.596872 -0.819318 + 2 C 6.0000 0 12.011 -2.432081 0.018160 -0.117959 + 3 H 1.0000 0 1.008 0.622838 -2.671266 -0.858069 + 4 H 1.0000 0 1.008 4.129338 -0.288244 1.238116 + 5 H 1.0000 0 1.008 1.944809 2.465949 1.771232 + 6 H 1.0000 0 1.008 0.739018 0.089159 -2.772193 + 7 H 1.0000 0 1.008 -2.896548 -0.695487 1.781244 + 8 H 1.0000 0 1.008 -3.746106 -0.860980 -1.475429 + 9 H 1.0000 0 1.008 -2.771617 2.072430 -0.132310 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.521300256600 0.00000000 0.00000000 + C 2 1 0 1.557219877906 112.95243568 0.00000000 + H 2 1 3 1.106763546254 109.25476666 238.05126840 + H 1 2 3 1.097243615790 120.10917125 154.79299118 + H 1 2 3 1.096936698891 120.47886746 321.33865099 + H 2 1 3 1.113646969559 109.68546909 121.70987737 + H 3 2 1 1.101399941323 110.94466480 300.12198739 + H 3 2 1 1.102705974257 110.77071881 180.18222188 + H 3 2 1 1.101847636143 111.05189540 60.18202749 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.874840852439 0.00000000 0.00000000 + C 2 1 0 2.942719099540 112.95243568 0.00000000 + H 2 1 3 2.091479997427 109.25476666 238.05126840 + H 1 2 3 2.073489936037 120.10917125 154.79299118 + H 1 2 3 2.072909947152 120.47886746 321.33865099 + H 2 1 3 2.104487782338 109.68546909 121.70987737 + H 3 2 1 2.081344253017 110.94466480 300.12198739 + H 3 2 1 2.083812297584 110.77071881 180.18222188 + H 3 2 1 2.082190273619 111.05189540 60.18202749 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1106 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.730797911198 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.154e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40932 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5301 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10978 +Total number of batches ... 90 +Average number of points per batch ... 121 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24087 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9576915966722339 0.00e+00 9.75e-04 5.14e-03 7.40e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9579159496278606 -2.24e-04 4.51e-04 3.62e-03 1.03e-03 0.1 + 3 -116.9579372658668746 -2.13e-05 1.68e-04 9.23e-04 4.54e-04 0.1 + 4 -116.9579399228804135 -2.66e-06 5.21e-05 3.77e-04 1.64e-04 0.1 + 5 -116.9579404041394781 -4.81e-07 9.26e-06 4.61e-05 1.61e-05 0.1 + 6 -116.9579404103620988 -6.22e-09 3.66e-06 1.78e-05 1.06e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.097 sec) +Old exchange energy : -3.614492587 Eh +New exchange energy : -3.614504364 Eh +Exchange energy change after final integration : -0.000011776 Eh +Total energy after final integration : -116.957952187 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95795218684447 Eh -3182.58768 eV + +Components: +Nuclear Repulsion : 74.73079791119845 Eh 2033.52839 eV +Electronic Energy : -191.68873832156055 Eh -5216.11575 eV +One Electron Energy: -304.52878269894757 Eh -8286.64946 eV +Two Electron Energy: 112.84004437738703 Eh 3070.53371 eV + +Virial components: +Potential Energy : -232.15700280817254 Eh -6317.31321 eV +Kinetic Energy : 115.19905062132807 Eh 3134.72553 eV +Virial Ratio : 2.01526836858489 + +DFT components: +N(Alpha) : 13.000010599433 electrons +N(Beta) : 12.000010333195 electrons +N(Total) : 25.000020932628 electrons +E(X) : -14.263805182423 Eh +E(C) : -0.914889567719 Eh +E(XC) : -15.178694750142 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.2226e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.7834e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.6603e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.3454e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.0636e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.0184e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754397 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004397 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.7 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.957952186844 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000942528 0.000353109 -0.001992521 + 2 C : -0.003006286 0.000160899 0.001193473 + 3 C : 0.004631740 -0.000758011 0.000068150 + 4 H : 0.000268982 -0.000859709 0.000644628 + 5 H : 0.000848441 -0.000925343 0.000210252 + 6 H : -0.000091479 0.000636673 0.000784155 + 7 H : 0.001692556 0.001089308 -0.001107242 + 8 H : -0.000929065 0.000166183 0.000237736 + 9 H : -0.001332334 -0.000226998 -0.000218018 + 10 H : -0.001140027 0.000363888 0.000179387 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000131166 0.0000226708 0.0000069773 + +Norm of the Cartesian gradient ... 0.0071373963 +RMS gradient ... 0.0013031043 +MAX gradient ... 0.0046317398 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.670 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 17.5%) +COSX gradient .... 0.424 sec ( 63.4%) +XC gradient .... 0.122 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 35 +Current Energy .... -116.957952187 Eh +Current gradient norm .... 0.007137396 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.300 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999035829 +Lowest eigenvalues of augmented Hessian: + -0.000099716 0.011981784 0.013751711 0.016525135 0.104214694 +Length of the computed step .... 0.043944671 +The final length of the internal step .... 0.043944671 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0074280051 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0076446714 RMS(Int)= 1.0610126666 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000049954 +Previously predicted energy change .... -0.002591972 +Actually observed energy change .... -0.002522598 +Ratio of predicted to observed change .... 0.973234757 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0025225977 0.0000050000 NO + RMS gradient 0.0007946611 0.0001000000 NO + MAX gradient 0.0016878430 0.0003000000 NO + RMS step 0.0074280051 0.0020000000 NO + MAX step 0.0226866240 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0023 Max(Angles) 0.36 + Max(Dihed) 1.30 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5213 -0.000728 0.0015 1.5228 + 2. B(C 2,C 1) 1.5572 -0.001199 0.0023 1.5596 + 3. B(H 3,C 1) 1.1068 0.000875 -0.0011 1.1056 + 4. B(H 4,C 0) 1.0972 0.001172 -0.0015 1.0958 + 5. B(H 5,C 0) 1.0969 0.000888 -0.0011 1.0959 + 6. B(H 6,C 1) 1.1136 0.001688 -0.0022 1.1114 + 7. B(H 7,C 2) 1.1014 0.000367 -0.0004 1.1010 + 8. B(H 8,C 2) 1.1027 0.001078 -0.0015 1.1012 + 9. B(H 9,C 2) 1.1018 0.000544 -0.0007 1.1011 + 10. A(H 4,C 0,H 5) 118.07 0.000081 -0.15 117.93 + 11. A(C 1,C 0,H 4) 120.11 -0.000566 -0.00 120.11 + 12. A(C 1,C 0,H 5) 120.48 0.000664 -0.23 120.25 + 13. A(C 0,C 1,H 3) 109.25 -0.000502 0.18 109.44 + 14. A(C 2,C 1,H 3) 109.35 -0.000177 0.03 109.39 + 15. A(C 0,C 1,C 2) 112.95 0.000515 -0.03 112.92 + 16. A(H 3,C 1,H 6) 106.46 0.000198 -0.14 106.32 + 17. A(C 2,C 1,H 6) 108.93 0.001367 -0.36 108.57 + 18. A(C 0,C 1,H 6) 109.69 -0.001414 0.30 109.99 + 19. A(H 7,C 2,H 9) 107.95 -0.000876 0.15 108.10 + 20. A(C 1,C 2,H 9) 111.05 0.001192 -0.24 110.81 + 21. A(H 7,C 2,H 8) 108.00 -0.000933 0.20 108.21 + 22. A(C 1,C 2,H 8) 110.77 0.000663 -0.11 110.66 + 23. A(H 8,C 2,H 9) 107.99 -0.001117 0.20 108.19 + 24. A(C 1,C 2,H 7) 110.94 0.000926 -0.17 110.77 + 25. D(C 2,C 1,C 0,H 5) -38.66 0.000230 -1.15 -39.81 + 26. D(H 3,C 1,C 0,H 5) -160.61 0.000468 -1.30 -161.91 + 27. D(C 2,C 1,C 0,H 4) 154.79 -0.000668 0.93 155.72 + 28. D(H 6,C 1,C 0,H 4) -83.50 0.000420 0.67 -82.83 + 29. D(H 3,C 1,C 0,H 4) 32.84 -0.000430 0.78 33.62 + 30. D(H 7,C 2,C 1,H 3) 62.01 -0.000445 -0.05 61.96 + 31. D(H 7,C 2,C 1,C 0) -59.88 -0.000025 -0.29 -60.17 + 32. D(H 8,C 2,C 1,H 3) -57.93 -0.000319 -0.12 -58.05 + 33. D(H 8,C 2,C 1,C 0) -179.82 0.000101 -0.36 -180.18 + 34. D(H 8,C 2,C 1,H 6) 58.05 0.000583 -0.48 57.57 + 35. D(H 7,C 2,C 1,H 6) 177.99 0.000457 -0.41 177.58 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (11.890 %) +Internal coordinates : 0.000 s ( 1.968 %) +B/P matrices and projection : 0.000 s (16.933 %) +Hessian update/contruction : 0.001 s (24.436 %) +Making the step : 0.000 s (13.079 %) +Converting the step to Cartesian: 0.000 s ( 2.501 %) +Storing new data : 0.000 s ( 1.927 %) +Checking convergence : 0.000 s ( 0.820 %) +Final printing : 0.001 s (26.363 %) +Total time : 0.002 s + +Time for energy+gradient : 5.464 s +Time for complete geometry iter : 6.312 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.192027 0.296931 0.537756 + C 0.190290 -0.318037 -0.430294 + C -1.289516 0.009054 -0.062344 + H 0.328427 -1.414734 -0.455303 + H 2.187229 -0.146730 0.653789 + H 1.033011 1.308790 0.927363 + H 0.386956 0.045023 -1.462180 + H -1.536625 -0.374444 0.939638 + H -1.980520 -0.450035 -0.786526 + H -1.461980 1.096605 -0.064439 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.252605 0.561118 1.016211 + 1 C 6.0000 0 12.011 0.359595 -0.601002 -0.813137 + 2 C 6.0000 0 12.011 -2.436832 0.017110 -0.117813 + 3 H 1.0000 0 1.008 0.620636 -2.673460 -0.860398 + 4 H 1.0000 0 1.008 4.133264 -0.277280 1.235481 + 5 H 1.0000 0 1.008 1.952107 2.473255 1.752463 + 6 H 1.0000 0 1.008 0.731241 0.085082 -2.763120 + 7 H 1.0000 0 1.008 -2.903800 -0.707596 1.775658 + 8 H 1.0000 0 1.008 -3.742640 -0.850442 -1.486320 + 9 H 1.0000 0 1.008 -2.762741 2.072283 -0.121772 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522754827316 0.00000000 0.00000000 + C 2 1 0 1.559551145078 112.92453406 0.00000000 + H 2 1 3 1.105645659737 109.43720483 237.89921721 + H 1 2 3 1.095775912909 120.08410668 155.72003740 + H 1 2 3 1.095873933910 120.22834479 320.19255078 + H 2 1 3 1.111431354377 109.99247098 121.45191227 + H 3 2 1 1.100955045871 110.77130934 299.83152662 + H 3 2 1 1.101221667655 110.65947172 179.82201137 + H 3 2 1 1.101142090079 110.81246023 59.80281338 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.877589592733 0.00000000 0.00000000 + C 2 1 0 2.947124556040 112.92453406 0.00000000 + H 2 1 3 2.089367498062 109.43720483 237.89921721 + H 1 2 3 2.070716379545 120.08410668 155.72003740 + H 1 2 3 2.070901612393 120.22834479 320.19255078 + H 2 1 3 2.100300876426 109.99247098 121.45191227 + H 3 2 1 2.080503522455 110.77130934 299.83152662 + H 3 2 1 2.081007364608 110.65947172 179.82201137 + H 3 2 1 2.080856984783 110.81246023 59.80281338 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1106 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.716226022373 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.153e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40934 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5301 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10977 +Total number of batches ... 91 +Average number of points per batch ... 120 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24087 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9579470702054920 0.00e+00 4.73e-04 4.92e-03 6.73e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9579969208715369 -4.99e-05 2.90e-04 3.10e-03 9.58e-04 0.1 + 3 -116.9580083432163491 -1.14e-05 8.79e-05 9.10e-04 3.16e-04 0.1 + 4 -116.9580091303565581 -7.87e-07 1.20e-05 5.85e-05 2.77e-05 0.1 + 5 -116.9580091374220530 -7.07e-09 4.82e-06 2.34e-05 1.92e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.097 sec) +Old exchange energy : -3.614716488 Eh +New exchange energy : -3.614729354 Eh +Exchange energy change after final integration : -0.000012866 Eh +Total energy after final integration : -116.958022003 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95802200349749 Eh -3182.58958 eV + +Components: +Nuclear Repulsion : 74.71622602237296 Eh 2033.13187 eV +Electronic Energy : -191.67423515979502 Eh -5215.72110 eV +One Electron Energy: -304.49466839448985 Eh -8285.72116 eV +Two Electron Energy: 112.82043323469483 Eh 3070.00006 eV + +Virial components: +Potential Energy : -232.16009920963089 Eh -6317.39747 eV +Kinetic Energy : 115.20207720613340 Eh 3134.80789 eV +Virial Ratio : 2.01524230152745 + +DFT components: +N(Alpha) : 13.000012111384 electrons +N(Beta) : 12.000011727071 electrons +N(Total) : 25.000023838455 electrons +E(X) : -14.264476586459 Eh +E(C) : -0.914898899625 Eh +E(XC) : -15.179375486085 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.0655e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.3362e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.8240e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.5516e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.9217e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2918e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754334 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004334 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.958022003497 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000631923 0.000807362 -0.000396171 + 2 C : -0.001411063 -0.000398388 -0.000177812 + 3 C : 0.001624007 -0.000352948 -0.000501926 + 4 H : 0.000092682 -0.000061111 0.000152578 + 5 H : -0.000240185 -0.000158120 0.000086893 + 6 H : 0.000122508 -0.000234680 0.000296273 + 7 H : 0.000584636 0.000186477 0.000090780 + 8 H : -0.000377223 0.000118896 0.000046953 + 9 H : -0.000432614 0.000113822 0.000278075 + 10 H : -0.000594672 -0.000021311 0.000124358 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000112392 0.0000219133 0.0000053945 + +Norm of the Cartesian gradient ... 0.0028067047 +RMS gradient ... 0.0005124318 +MAX gradient ... 0.0016240074 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.650 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.115 sec ( 17.7%) +COSX gradient .... 0.410 sec ( 63.1%) +XC gradient .... 0.119 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.7 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 35 +Current Energy .... -116.958022003 Eh +Current gradient norm .... 0.002806705 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.998468551 +Lowest eigenvalues of augmented Hessian: + -0.000048142 0.010461394 0.012785065 0.013754546 0.103210439 +Length of the computed step .... 0.055407117 +The final length of the internal step .... 0.055407117 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0093655122 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0096006523 RMS(Int)= 0.0093486057 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000024145 +Previously predicted energy change .... -0.000049954 +Actually observed energy change .... -0.000069817 +Ratio of predicted to observed change .... 1.397610337 +New trust radius .... 0.450000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000698167 0.0000050000 NO + RMS gradient 0.0003287562 0.0001000000 NO + MAX gradient 0.0006862967 0.0003000000 NO + RMS step 0.0093655122 0.0020000000 NO + MAX step 0.0290614226 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.34 + Max(Dihed) 1.67 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5228 0.000498 -0.0003 1.5224 + 2. B(C 2,C 1) 1.5596 -0.000251 0.0015 1.5611 + 3. B(H 3,C 1) 1.1056 0.000069 -0.0003 1.1053 + 4. B(H 4,C 0) 1.0958 -0.000145 0.0002 1.0959 + 5. B(H 5,C 0) 1.0959 -0.000129 0.0002 1.0961 + 6. B(H 6,C 1) 1.1114 0.000080 -0.0005 1.1109 + 7. B(H 7,C 2) 1.1010 0.000085 -0.0002 1.1007 + 8. B(H 8,C 2) 1.1012 0.000041 -0.0003 1.1009 + 9. B(H 9,C 2) 1.1011 0.000072 -0.0003 1.1009 + 10. A(H 4,C 0,H 5) 117.90 -0.000074 -0.17 117.73 + 11. A(C 1,C 0,H 4) 120.08 -0.000294 -0.05 120.03 + 12. A(C 1,C 0,H 5) 120.23 0.000502 -0.34 119.89 + 13. A(C 0,C 1,H 3) 109.44 -0.000270 0.17 109.60 + 14. A(C 2,C 1,H 3) 109.39 -0.000112 0.03 109.41 + 15. A(C 0,C 1,C 2) 112.92 0.000467 -0.11 112.81 + 16. A(H 3,C 1,H 6) 106.31 0.000013 -0.06 106.26 + 17. A(C 2,C 1,H 6) 108.57 0.000518 -0.31 108.26 + 18. A(C 0,C 1,H 6) 109.99 -0.000636 0.28 110.27 + 19. A(H 7,C 2,H 9) 108.10 -0.000505 0.17 108.27 + 20. A(C 1,C 2,H 9) 110.81 0.000686 -0.28 110.53 + 21. A(H 7,C 2,H 8) 108.21 -0.000485 0.22 108.43 + 22. A(C 1,C 2,H 8) 110.66 0.000521 -0.17 110.49 + 23. A(H 8,C 2,H 9) 108.19 -0.000579 0.21 108.41 + 24. A(C 1,C 2,H 7) 110.77 0.000293 -0.13 110.64 + 25. D(C 2,C 1,C 0,H 5) -39.81 0.000225 -1.59 -41.39 + 26. D(H 3,C 1,C 0,H 5) -161.91 0.000246 -1.67 -163.57 + 27. D(C 2,C 1,C 0,H 4) 155.72 -0.000332 1.14 156.86 + 28. D(H 6,C 1,C 0,H 4) -82.83 0.000196 0.87 -81.95 + 29. D(H 3,C 1,C 0,H 4) 33.62 -0.000312 1.06 34.68 + 30. D(H 7,C 2,C 1,H 3) 61.96 -0.000114 -0.21 61.75 + 31. D(H 7,C 2,C 1,C 0) -60.17 -0.000004 -0.37 -60.54 + 32. D(H 8,C 2,C 1,H 3) -58.05 -0.000039 -0.30 -58.34 + 33. D(H 8,C 2,C 1,C 0) 179.82 0.000070 -0.45 179.37 + 34. D(H 8,C 2,C 1,H 6) 57.57 0.000201 -0.52 57.05 + 35. D(H 7,C 2,C 1,H 6) 177.58 0.000126 -0.44 177.14 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (17.237 %) +Internal coordinates : 0.000 s ( 1.930 %) +B/P matrices and projection : 0.000 s (16.754 %) +Hessian update/contruction : 0.000 s (14.956 %) +Making the step : 0.000 s (12.412 %) +Converting the step to Cartesian: 0.000 s ( 2.368 %) +Storing new data : 0.000 s ( 1.974 %) +Checking convergence : 0.000 s ( 0.877 %) +Final printing : 0.001 s (31.316 %) +Total time : 0.002 s + +Time for energy+gradient : 5.352 s +Time for complete geometry iter : 6.223 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.188122 0.292833 0.546664 + C 0.190565 -0.320508 -0.426201 + C -1.291201 0.008371 -0.061287 + H 0.327101 -1.417008 -0.455281 + H 2.188946 -0.141285 0.651387 + H 1.035288 1.314525 0.912973 + H 0.384367 0.044478 -1.457422 + H -1.540988 -0.382774 0.936800 + H -1.977740 -0.443166 -0.793883 + H -1.455162 1.096958 -0.056292 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.245225 0.553374 1.033045 + 1 C 6.0000 0 12.011 0.360116 -0.605673 -0.805403 + 2 C 6.0000 0 12.011 -2.440016 0.015819 -0.115815 + 3 H 1.0000 0 1.008 0.618132 -2.677757 -0.860356 + 4 H 1.0000 0 1.008 4.136508 -0.266990 1.230943 + 5 H 1.0000 0 1.008 1.956411 2.484093 1.725269 + 6 H 1.0000 0 1.008 0.726349 0.084052 -2.754128 + 7 H 1.0000 0 1.008 -2.912046 -0.723337 1.770296 + 8 H 1.0000 0 1.008 -3.737386 -0.837462 -1.500222 + 9 H 1.0000 0 1.008 -2.749858 2.072950 -0.106376 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522423266167 0.00000000 0.00000000 + C 2 1 0 1.561074922815 112.81154991 0.00000000 + H 2 1 3 1.105349964254 109.60413802 237.82007282 + H 1 2 3 1.095935004981 119.99044928 156.86077636 + H 1 2 3 1.096082359178 119.84963890 318.61179884 + H 2 1 3 1.110941303575 110.27359056 121.18199406 + H 3 2 1 1.100711512326 110.64048783 299.46026849 + H 3 2 1 1.100871992179 110.48601101 179.36944749 + H 3 2 1 1.100876909837 110.53344180 59.38027751 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.876963032966 0.00000000 0.00000000 + C 2 1 0 2.950004078653 112.81154991 0.00000000 + H 2 1 3 2.088808714579 109.60413802 237.82007282 + H 1 2 3 2.071017019991 119.99044928 156.86077636 + H 1 2 3 2.071295479068 119.84963890 318.61179884 + H 2 1 3 2.099374814618 110.27359056 121.18199406 + H 3 2 1 2.080043310751 110.64048783 299.46026849 + H 3 2 1 2.080346573723 110.48601101 179.36944749 + H 3 2 1 2.080355866750 110.53344180 59.38027751 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1106 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.721398620359 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.153e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40931 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5301 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10975 +Total number of batches ... 91 +Average number of points per batch ... 120 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24087 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9579279257284981 0.00e+00 6.22e-04 6.52e-03 9.32e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9580124997885235 -8.46e-05 3.81e-04 4.10e-03 1.31e-03 0.1 + 3 -116.9580320222082293 -1.95e-05 1.13e-04 1.18e-03 4.06e-04 0.1 + 4 -116.9580333753334997 -1.35e-06 6.74e-06 4.53e-05 1.65e-05 0.1 + 5 -116.9580333800295335 -4.70e-09 2.32e-06 1.82e-05 9.42e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.104 sec) +Old exchange energy : -3.614763312 Eh +New exchange energy : -3.614778311 Eh +Exchange energy change after final integration : -0.000014999 Eh +Total energy after final integration : -116.958048379 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95804837892094 Eh -3182.59030 eV + +Components: +Nuclear Repulsion : 74.72139862035901 Eh 2033.27263 eV +Electronic Energy : -191.67943200038854 Eh -5215.86251 eV +One Electron Energy: -304.50405616401770 Eh -8285.97662 eV +Two Electron Energy: 112.82462416362915 Eh 3070.11411 eV + +Virial components: +Potential Energy : -232.16162280182823 Eh -6317.43893 eV +Kinetic Energy : 115.20357442290731 Eh 3134.84863 eV +Virial Ratio : 2.01522933611047 + +DFT components: +N(Alpha) : 13.000013890967 electrons +N(Beta) : 12.000013388059 electrons +N(Total) : 25.000027279026 electrons +E(X) : -14.264612409962 Eh +E(C) : -0.914883262229 Eh +E(XC) : -15.179495672191 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.6960e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.8232e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.3179e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.0796e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 9.4164e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.3847e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754250 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004250 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.958048378921 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000372097 0.000391176 0.000212029 + 2 C : 0.000130621 -0.000242179 -0.000155599 + 3 C : -0.000329454 0.000090844 -0.000333062 + 4 H : -0.000005051 0.000113239 -0.000109493 + 5 H : -0.000251146 0.000046524 -0.000006764 + 6 H : 0.000092446 -0.000232912 0.000021371 + 7 H : -0.000200087 -0.000144777 0.000215203 + 8 H : 0.000110671 0.000015087 0.000005768 + 9 H : 0.000069869 0.000029108 0.000115274 + 10 H : 0.000010035 -0.000066111 0.000035274 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000094495 0.0000226026 0.0000028610 + +Norm of the Cartesian gradient ... 0.0009808158 +RMS gradient ... 0.0001790716 +MAX gradient ... 0.0003911756 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.694 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.006 sec ( 0.8%) +RI-J Coulomb gradient .... 0.120 sec ( 17.3%) +COSX gradient .... 0.444 sec ( 63.9%) +XC gradient .... 0.124 sec ( 17.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 35 +Current Energy .... -116.958048379 Eh +Current gradient norm .... 0.000980816 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.450 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999944676 +Lowest eigenvalues of augmented Hessian: + -0.000002373 0.009071490 0.012685815 0.013753625 0.104134917 +Length of the computed step .... 0.010519399 +The final length of the internal step .... 0.010519399 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0017781029 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0019985638 RMS(Int)= 0.0017770133 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000001187 +Previously predicted energy change .... -0.000024145 +Actually observed energy change .... -0.000026375 +Ratio of predicted to observed change .... 1.092374349 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000263754 0.0000050000 NO + RMS gradient 0.0001260657 0.0001000000 NO + MAX gradient 0.0003678347 0.0003000000 NO + RMS step 0.0017781029 0.0020000000 YES + MAX step 0.0051578372 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.07 + Max(Dihed) 0.30 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5224 0.000368 -0.0004 1.5220 + 2. B(C 2,C 1) 1.5611 0.000104 -0.0000 1.5611 + 3. B(H 3,C 1) 1.1053 -0.000110 0.0001 1.1054 + 4. B(H 4,C 0) 1.0959 -0.000249 0.0003 1.0962 + 5. B(H 5,C 0) 1.0961 -0.000223 0.0003 1.0964 + 6. B(H 6,C 1) 1.1109 -0.000283 0.0003 1.1112 + 7. B(H 7,C 2) 1.1007 -0.000026 0.0000 1.1007 + 8. B(H 8,C 2) 1.1009 -0.000132 0.0001 1.1010 + 9. B(H 9,C 2) 1.1009 -0.000067 0.0001 1.1009 + 10. A(H 4,C 0,H 5) 117.69 -0.000046 -0.03 117.66 + 11. A(C 1,C 0,H 4) 119.99 -0.000104 -0.01 119.98 + 12. A(C 1,C 0,H 5) 119.85 0.000174 -0.07 119.78 + 13. A(C 0,C 1,H 3) 109.60 -0.000018 0.00 109.61 + 14. A(C 2,C 1,H 3) 109.41 0.000008 -0.00 109.41 + 15. A(C 0,C 1,C 2) 112.81 0.000101 -0.03 112.78 + 16. A(H 3,C 1,H 6) 106.26 -0.000044 0.02 106.28 + 17. A(C 2,C 1,H 6) 108.26 -0.000171 0.02 108.28 + 18. A(C 0,C 1,H 6) 110.27 0.000113 -0.01 110.27 + 19. A(H 7,C 2,H 9) 108.27 -0.000025 0.02 108.28 + 20. A(C 1,C 2,H 9) 110.53 0.000033 -0.03 110.51 + 21. A(H 7,C 2,H 8) 108.43 0.000048 0.01 108.44 + 22. A(C 1,C 2,H 8) 110.49 0.000082 -0.02 110.46 + 23. A(H 8,C 2,H 9) 108.40 0.000056 0.00 108.41 + 24. A(C 1,C 2,H 7) 110.64 -0.000190 0.02 110.66 + 25. D(C 2,C 1,C 0,H 5) -41.39 0.000085 -0.30 -41.68 + 26. D(H 3,C 1,C 0,H 5) -163.57 0.000017 -0.27 -163.84 + 27. D(C 2,C 1,C 0,H 4) 156.86 0.000010 0.19 157.05 + 28. D(H 6,C 1,C 0,H 4) -81.96 -0.000059 0.18 -81.77 + 29. D(H 3,C 1,C 0,H 4) 34.68 -0.000058 0.21 34.89 + 30. D(H 7,C 2,C 1,H 3) 61.75 0.000076 -0.12 61.63 + 31. D(H 7,C 2,C 1,C 0) -60.54 0.000024 -0.10 -60.64 + 32. D(H 8,C 2,C 1,H 3) -58.34 0.000086 -0.13 -58.47 + 33. D(H 8,C 2,C 1,C 0) 179.37 0.000034 -0.11 179.26 + 34. D(H 8,C 2,C 1,H 6) 57.05 -0.000055 -0.09 56.96 + 35. D(H 7,C 2,C 1,H 6) 177.14 -0.000065 -0.08 177.06 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (19.215 %) +Internal coordinates : 0.000 s ( 2.027 %) +B/P matrices and projection : 0.000 s (16.427 %) +Hessian update/contruction : 0.000 s (12.458 %) +Making the step : 0.000 s (11.824 %) +Converting the step to Cartesian: 0.000 s ( 2.407 %) +Storing new data : 0.000 s ( 1.816 %) +Checking convergence : 0.000 s ( 0.802 %) +Final printing : 0.001 s (32.897 %) +Total time : 0.002 s + +Time for energy+gradient : 5.431 s +Time for complete geometry iter : 6.420 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.187164 0.292025 0.547863 + C 0.190549 -0.320927 -0.425561 + C -1.291203 0.008189 -0.060856 + H 0.326857 -1.417549 -0.454635 + H 2.189189 -0.140480 0.650692 + H 1.035276 1.315690 0.909836 + H 0.385116 0.044613 -1.456756 + H -1.542271 -0.384640 0.936254 + H -1.977303 -0.441482 -0.795167 + H -1.454075 1.096985 -0.054212 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.243415 0.551847 1.035310 + 1 C 6.0000 0 12.011 0.360085 -0.606465 -0.804193 + 2 C 6.0000 0 12.011 -2.440019 0.015476 -0.115001 + 3 H 1.0000 0 1.008 0.617670 -2.678779 -0.859136 + 4 H 1.0000 0 1.008 4.136969 -0.265468 1.229630 + 5 H 1.0000 0 1.008 1.956388 2.486293 1.719341 + 6 H 1.0000 0 1.008 0.727763 0.084307 -2.752869 + 7 H 1.0000 0 1.008 -2.914470 -0.726865 1.769264 + 8 H 1.0000 0 1.008 -3.736561 -0.834281 -1.502647 + 9 H 1.0000 0 1.008 -2.747804 2.073002 -0.102446 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.522007025877 0.00000000 0.00000000 + C 2 1 0 1.561062178527 112.78100291 0.00000000 + H 2 1 3 1.105442486145 109.60857516 237.84190937 + H 1 2 3 1.096215964086 119.97627514 157.04906691 + H 1 2 3 1.096350480766 119.76676868 318.31746224 + H 2 1 3 1.111233196655 110.26563055 121.17757393 + H 3 2 1 1.100717269881 110.66484194 299.35721584 + H 3 2 1 1.100977473795 110.46190479 179.25647417 + H 3 2 1 1.100930619910 110.50807603 59.29645248 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.876176452811 0.00000000 0.00000000 + C 2 1 0 2.949979995439 112.78100291 0.00000000 + H 2 1 3 2.088983555616 109.60857516 237.84190937 + H 1 2 3 2.071547955756 119.97627514 157.04906691 + H 1 2 3 2.071802155441 119.76676868 318.31746224 + H 2 1 3 2.099926412600 110.26563055 121.17757393 + H 3 2 1 2.080054190952 110.66484194 299.35721584 + H 3 2 1 2.080545905090 110.46190479 179.25647417 + H 3 2 1 2.080457364079 110.50807603 59.29645248 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1106 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.726617672260 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.153e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40930 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5299 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10973 +Total number of batches ... 91 +Average number of points per batch ... 120 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24088 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9580306103555216 0.00e+00 1.15e-04 1.15e-03 1.72e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9580336530054723 -3.04e-06 6.94e-05 7.27e-04 2.40e-04 0.1 + 3 -116.9580343210844120 -6.68e-07 2.05e-05 2.05e-04 7.20e-05 0.1 + 4 -116.9580343659700787 -4.49e-08 2.04e-06 1.15e-05 4.03e-06 0.1 + 5 -116.9580343652883556 6.82e-10 7.46e-07 3.92e-06 2.72e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 5 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.102 sec) +Old exchange energy : -3.614745310 Eh +New exchange energy : -3.614760914 Eh +Exchange energy change after final integration : -0.000015604 Eh +Total energy after final integration : -116.958049969 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95804996908434 Eh -3182.59034 eV + +Components: +Nuclear Repulsion : 74.72661767225959 Eh 2033.41464 eV +Electronic Energy : -191.68465203754795 Eh -5216.00456 eV +One Electron Energy: -304.51482844612957 Eh -8286.26975 eV +Two Electron Energy: 112.83017640858164 Eh 3070.26519 eV + +Virial components: +Potential Energy : -232.16161440941315 Eh -6317.43870 eV +Kinetic Energy : 115.20356444032880 Eh 3134.84836 eV +Virial Ratio : 2.01522943788483 + +DFT components: +N(Alpha) : 13.000014122620 electrons +N(Beta) : 12.000013605519 electrons +N(Total) : 25.000027728139 electrons +E(X) : -14.264556261679 Eh +E(C) : -0.914878617043 Eh +E(XC) : -15.179434878722 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... -6.8172e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 3.9248e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 7.4552e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.7437e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.7159e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.0192e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754236 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004236 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.9 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.958049969084 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000019222 0.000106048 0.000043049 + 2 C : 0.000228649 -0.000070803 0.000044875 + 3 C : -0.000272882 0.000067817 -0.000113502 + 4 H : -0.000000629 0.000037780 -0.000055709 + 5 H : -0.000073639 -0.000007072 -0.000010480 + 6 H : 0.000033552 -0.000064408 0.000012398 + 7 H : -0.000125300 -0.000045234 0.000028732 + 8 H : 0.000076033 0.000006877 0.000011548 + 9 H : 0.000064891 -0.000012348 0.000028690 + 10 H : 0.000050102 -0.000018659 0.000010400 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 0.0000000000 + +Difference to rotation invariance: + : 0.0000050793 0.0000242507 0.0000031948 + +Norm of the Cartesian gradient ... 0.0004614652 +RMS gradient ... 0.0000842516 +MAX gradient ... 0.0002728817 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.670 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.7%) +RI-J Coulomb gradient .... 0.117 sec ( 17.5%) +COSX gradient .... 0.419 sec ( 62.5%) +XC gradient .... 0.128 sec ( 19.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 35 +Current Energy .... -116.958049969 Eh +Current gradient norm .... 0.000461465 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.675 +Updating the Hessian (BFGS) .... done +Forming the augmented Hessian .... done +Diagonalizing the augmented Hessian .... done +Last element of RFO vector .... 0.999981804 +Lowest eigenvalues of augmented Hessian: + -0.000000682 0.007528495 0.013017020 0.013763050 0.102080903 +Length of the computed step .... 0.006032636 +The final length of the internal step .... 0.006032636 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0010197016 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0012774825 RMS(Int)= 0.0010196413 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000341 +Previously predicted energy change .... -0.000001187 +Actually observed energy change .... -0.000001590 +Ratio of predicted to observed change .... 1.340187596 +New trust radius .... 0.675000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000015902 0.0000050000 YES + RMS gradient 0.0000505367 0.0001000000 YES + MAX gradient 0.0001152670 0.0003000000 YES + RMS step 0.0010197016 0.0020000000 YES + MAX step 0.0020997837 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.04 + Max(Dihed) 0.12 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5220 0.000030 -0.0001 1.5219 + 2. B(C 2,C 1) 1.5611 0.000072 -0.0001 1.5609 + 3. B(H 3,C 1) 1.1054 -0.000036 0.0001 1.1055 + 4. B(H 4,C 0) 1.0962 -0.000066 0.0001 1.0963 + 5. B(H 5,C 0) 1.0964 -0.000060 0.0001 1.0965 + 6. B(H 6,C 1) 1.1112 -0.000064 0.0001 1.1114 + 7. B(H 7,C 2) 1.1007 -0.000010 0.0000 1.1007 + 8. B(H 8,C 2) 1.1010 -0.000054 0.0001 1.1011 + 9. B(H 9,C 2) 1.1009 -0.000026 0.0000 1.1010 + 10. A(H 4,C 0,H 5) 117.65 -0.000007 -0.02 117.63 + 11. A(C 1,C 0,H 4) 119.98 -0.000065 0.00 119.98 + 12. A(C 1,C 0,H 5) 119.77 0.000075 -0.04 119.72 + 13. A(C 0,C 1,H 3) 109.61 0.000001 -0.01 109.60 + 14. A(C 2,C 1,H 3) 109.41 0.000019 -0.01 109.40 + 15. A(C 0,C 1,C 2) 112.78 0.000005 -0.01 112.77 + 16. A(H 3,C 1,H 6) 106.28 -0.000017 0.02 106.30 + 17. A(C 2,C 1,H 6) 108.28 -0.000115 0.04 108.32 + 18. A(C 0,C 1,H 6) 110.27 0.000105 -0.03 110.23 + 19. A(H 7,C 2,H 9) 108.28 0.000024 -0.00 108.28 + 20. A(C 1,C 2,H 9) 110.51 -0.000039 0.01 110.51 + 21. A(H 7,C 2,H 8) 108.44 0.000060 -0.01 108.42 + 22. A(C 1,C 2,H 8) 110.46 -0.000017 0.00 110.46 + 23. A(H 8,C 2,H 9) 108.41 0.000075 -0.02 108.39 + 24. A(C 1,C 2,H 7) 110.66 -0.000098 0.03 110.69 + 25. D(C 2,C 1,C 0,H 5) -41.68 0.000029 -0.12 -41.80 + 26. D(H 3,C 1,C 0,H 5) -163.84 -0.000001 -0.10 -163.94 + 27. D(C 2,C 1,C 0,H 4) 157.05 0.000019 0.09 157.14 + 28. D(H 6,C 1,C 0,H 4) -81.77 -0.000051 0.11 -81.66 + 29. D(H 3,C 1,C 0,H 4) 34.89 -0.000010 0.11 35.00 + 30. D(H 7,C 2,C 1,H 3) 61.63 0.000042 -0.11 61.51 + 31. D(H 7,C 2,C 1,C 0) -60.64 0.000024 -0.09 -60.74 + 32. D(H 8,C 2,C 1,H 3) -58.47 0.000041 -0.11 -58.59 + 33. D(H 8,C 2,C 1,C 0) 179.26 0.000023 -0.10 179.16 + 34. D(H 8,C 2,C 1,H 6) 56.96 -0.000032 -0.07 56.88 + 35. D(H 7,C 2,C 1,H 6) 177.06 -0.000031 -0.07 176.98 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (20.565 %) +Internal coordinates : 0.000 s ( 1.824 %) +B/P matrices and projection : 0.000 s (15.415 %) +Hessian update/contruction : 0.000 s (13.591 %) +Making the step : 0.000 s (10.873 %) +Converting the step to Cartesian: 0.000 s ( 2.003 %) +Storing new data : 0.000 s ( 1.717 %) +Checking convergence : 0.000 s ( 0.751 %) +Final printing : 0.001 s (33.119 %) +Total time : 0.003 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 5 CYCLES) *** + ******************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C 1.186849 0.291760 0.548240 + C 0.190459 -0.321200 -0.425264 + C -1.291135 0.008074 -0.060649 + H 0.326627 -1.417910 -0.453930 + H 2.189485 -0.139862 0.650206 + H 1.035271 1.316323 0.908179 + H 0.385916 0.044409 -1.456394 + H -1.543257 -0.385963 0.935731 + H -1.977258 -0.440165 -0.795961 + H -1.453658 1.096959 -0.052699 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 2.242820 0.551347 1.036023 + 1 C 6.0000 0 12.011 0.359915 -0.606980 -0.803632 + 2 C 6.0000 0 12.011 -2.439892 0.015257 -0.114611 + 3 H 1.0000 0 1.008 0.617235 -2.679462 -0.857804 + 4 H 1.0000 0 1.008 4.137527 -0.264301 1.228712 + 5 H 1.0000 0 1.008 1.956379 2.487489 1.716210 + 6 H 1.0000 0 1.008 0.729276 0.083922 -2.752186 + 7 H 1.0000 0 1.008 -2.916333 -0.729364 1.768275 + 8 H 1.0000 0 1.008 -3.736476 -0.831791 -1.504148 + 9 H 1.0000 0 1.008 -2.747016 2.072952 -0.099588 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.521914489241 0.00000000 0.00000000 + C 2 1 0 1.560924503642 112.77074684 0.00000000 + H 2 1 3 1.105502988140 109.60289413 237.86024057 + H 1 2 3 1.096345663997 119.97788561 157.14070133 + H 1 2 3 1.096476200144 119.72348310 318.19733553 + H 2 1 3 1.111352270200 110.23324148 121.19569180 + H 3 2 1 1.100728395999 110.69165614 299.26245314 + H 3 2 1 1.101074394906 110.46291326 179.16125071 + H 3 2 1 1.100976110135 110.51380230 59.21966824 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.876001583912 0.00000000 0.00000000 + C 2 1 0 2.949719827611 112.77074684 0.00000000 + H 2 1 3 2.089097887816 109.60289413 237.86024057 + H 1 2 3 2.071793053066 119.97788561 157.14070133 + H 1 2 3 2.072039730635 119.72348310 318.19733553 + H 2 1 3 2.100151428990 110.23324148 121.19569180 + H 3 2 1 2.080075216268 110.69165614 299.26245314 + H 3 2 1 2.080729059446 110.46291326 179.16125071 + H 3 2 1 2.080543328145 110.51380230 59.21966824 + +--------------------- +BASIS SET INFORMATION +--------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 6s3p contracted to 2s1p pattern {33/3} + Group 2 Type H : 3s contracted to 1s pattern {3} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 +--------------------------------- +AUXILIARY/J BASIS SET INFORMATION +--------------------------------- +There are 2 groups of distinct atoms + + Group 1 Type C : 12s5p4d2f1g contracted to 6s4p3d1f1g pattern {711111/2111/211/2/1} + Group 2 Type H : 5s2p1d contracted to 3s1p1d pattern {311/2/1} + +Atom 0C basis set group => 1 +Atom 1C basis set group => 1 +Atom 2C basis set group => 1 +Atom 3H basis set group => 2 +Atom 4H basis set group => 2 +Atom 5H basis set group => 2 +Atom 6H basis set group => 2 +Atom 7H basis set group => 2 +Atom 8H basis set group => 2 +Atom 9H basis set group => 2 + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1106 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.728374657153 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.153e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40928 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5298 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10973 +Total number of batches ... 91 +Average number of points per batch ... 120 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24088 +Total number of batches ... 194 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input_product + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 74.7283746572 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input_product.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.9580332850772777 0.00e+00 5.89e-05 4.98e-04 7.58e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.9580341973581312 -9.12e-07 3.36e-05 3.15e-04 1.07e-04 0.1 + 3 -116.9580343695455724 -1.72e-07 9.39e-06 8.72e-05 3.30e-05 0.1 + 4 -116.9580343797883302 -1.02e-08 1.08e-06 6.52e-06 1.83e-06 0.1 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.614732891 Eh +New exchange energy : -3.614748897 Eh +Exchange energy change after final integration : -0.000016006 Eh +Total energy after final integration : -116.958050386 Eh + **** ENERGY FILE WAS UPDATED (input_product.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.95805038551754 Eh -3182.59035 eV + +Components: +Nuclear Repulsion : 74.72837465715270 Eh 2033.46245 eV +Electronic Energy : -191.68640903694103 Eh -5216.05237 eV +One Electron Energy: -304.51831012272049 Eh -8286.36449 eV +Two Electron Energy: 112.83190108577945 Eh 3070.31212 eV + +Virial components: +Potential Energy : -232.16156064022266 Eh -6317.43724 eV +Kinetic Energy : 115.20351025470511 Eh 3134.84689 eV +Virial Ratio : 2.01522991900970 + +DFT components: +N(Alpha) : 13.000014200973 electrons +N(Beta) : 12.000013680606 electrons +N(Total) : 25.000027881579 electrons +E(X) : -14.264513129978 Eh +E(C) : -0.914873911125 Eh +E(XC) : -15.179387041103 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.0243e-08 Tolerance : 1.0000e-08 + Last MAX-Density change ... 6.5211e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.0755e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9864e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8297e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 4.2650e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.754230 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.004230 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.012632 -272.4576 + 1 1.0000 -10.000056 -272.1154 + 2 1.0000 -9.964411 -271.1454 + 3 1.0000 -0.730776 -19.8854 + 4 1.0000 -0.629589 -17.1320 + 5 1.0000 -0.541339 -14.7306 + 6 1.0000 -0.412418 -11.2225 + 7 1.0000 -0.393831 -10.7167 + 8 1.0000 -0.360355 -9.8057 + 9 1.0000 -0.318408 -8.6643 + 10 1.0000 -0.303936 -8.2705 + 11 1.0000 -0.296923 -8.0797 + 12 1.0000 -0.134841 -3.6692 + 13 0.0000 0.373539 10.1645 + 14 0.0000 0.389038 10.5863 + 15 0.0000 0.410733 11.1766 + 16 0.0000 0.441871 12.0239 + 17 0.0000 0.466206 12.6861 + 18 0.0000 0.497166 13.5286 + 19 0.0000 0.503124 13.6907 + 20 0.0000 0.515651 14.0316 + 21 0.0000 0.559717 15.2307 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.013757 -272.4882 + 1 1.0000 -9.999706 -272.1058 + 2 1.0000 -9.948645 -270.7164 + 3 1.0000 -0.722052 -19.6480 + 4 1.0000 -0.610059 -16.6006 + 5 1.0000 -0.523750 -14.2520 + 6 1.0000 -0.407201 -11.0805 + 7 1.0000 -0.388211 -10.5638 + 8 1.0000 -0.354489 -9.6461 + 9 1.0000 -0.311632 -8.4799 + 10 1.0000 -0.297154 -8.0860 + 11 1.0000 -0.293661 -7.9909 + 12 0.0000 0.077230 2.1015 + 13 0.0000 0.381355 10.3772 + 14 0.0000 0.404685 11.0121 + 15 0.0000 0.414900 11.2900 + 16 0.0000 0.457568 12.4511 + 17 0.0000 0.472416 12.8551 + 18 0.0000 0.501797 13.6546 + 19 0.0000 0.507442 13.8082 + 20 0.0000 0.525917 14.3109 + 21 0.0000 0.572170 15.5695 +*Only the first 10 virtual orbitals were printed. + + ******************************** + * MULLIKEN POPULATION ANALYSIS * + ******************************** + +-------------------------------------------- +MULLIKEN ATOMIC CHARGES AND SPIN POPULATIONS +-------------------------------------------- + 0 C : -0.130126 1.091968 + 1 C : -0.138902 -0.074145 + 2 C : -0.214843 0.016900 + 3 H : 0.073036 0.011192 + 4 H : 0.061131 -0.046614 + 5 H : 0.060275 -0.046271 + 6 H : 0.072558 0.049490 + 7 H : 0.073187 -0.000935 + 8 H : 0.071967 -0.000616 + 9 H : 0.071717 -0.000969 +Sum of atomic charges : 0.0000000 +Sum of atomic spin populations: 1.0000000 + +----------------------------------------------------- +MULLIKEN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +----------------------------------------------------- +CHARGE + 0 C s : 3.216212 s : 3.216212 + pz : 0.975406 p : 2.913914 + px : 0.961308 + py : 0.977200 + + 1 C s : 3.186030 s : 3.186030 + pz : 0.991149 p : 2.952872 + px : 0.949999 + py : 1.011724 + + 2 C s : 3.195896 s : 3.195896 + pz : 1.026062 p : 3.018947 + px : 0.966558 + py : 1.026327 + + 3 H s : 0.926964 s : 0.926964 + + 4 H s : 0.938869 s : 0.938869 + + 5 H s : 0.939725 s : 0.939725 + + 6 H s : 0.927442 s : 0.927442 + + 7 H s : 0.926813 s : 0.926813 + + 8 H s : 0.928033 s : 0.928033 + + 9 H s : 0.928283 s : 0.928283 + + +SPIN + 0 C s : 0.083285 s : 0.083285 + pz : 0.632854 p : 1.008683 + px : 0.162939 + py : 0.212890 + + 1 C s : -0.015431 s : -0.015431 + pz : -0.027205 p : -0.058714 + px : -0.018638 + py : -0.012871 + + 2 C s : 0.003817 s : 0.003817 + pz : 0.001148 p : 0.013082 + px : 0.010009 + py : 0.001925 + + 3 H s : 0.011192 s : 0.011192 + + 4 H s : -0.046614 s : -0.046614 + + 5 H s : -0.046271 s : -0.046271 + + 6 H s : 0.049490 s : 0.049490 + + 7 H s : -0.000935 s : -0.000935 + + 8 H s : -0.000616 s : -0.000616 + + 9 H s : -0.000969 s : -0.000969 + + + + ******************************* + * LOEWDIN POPULATION ANALYSIS * + ******************************* + +------------------------------------------- +LOEWDIN ATOMIC CHARGES AND SPIN POPULATIONS +------------------------------------------- + 0 C : -0.075774 1.053717 + 1 C : -0.059937 -0.055870 + 2 C : -0.115697 0.015793 + 3 H : 0.037886 0.010220 + 4 H : 0.030177 -0.033860 + 5 H : 0.029444 -0.033578 + 6 H : 0.038193 0.045785 + 7 H : 0.039177 -0.000819 + 8 H : 0.038396 -0.000612 + 9 H : 0.038137 -0.000776 + +---------------------------------------------------- +LOEWDIN REDUCED ORBITAL CHARGES AND SPIN POPULATIONS +---------------------------------------------------- +CHARGE + 0 C s : 3.088321 s : 3.088321 + pz : 0.993524 p : 2.987453 + px : 0.991776 + py : 1.002153 + + 1 C s : 3.022946 s : 3.022946 + pz : 1.016029 p : 3.036991 + px : 0.987200 + py : 1.033762 + + 2 C s : 3.019045 s : 3.019045 + pz : 1.047906 p : 3.096652 + px : 1.000541 + py : 1.048205 + + 3 H s : 0.962114 s : 0.962114 + + 4 H s : 0.969823 s : 0.969823 + + 5 H s : 0.970556 s : 0.970556 + + 6 H s : 0.961807 s : 0.961807 + + 7 H s : 0.960823 s : 0.960823 + + 8 H s : 0.961604 s : 0.961604 + + 9 H s : 0.961863 s : 0.961863 + + +SPIN + 0 C s : 0.060077 s : 0.060077 + pz : 0.630086 p : 0.993640 + px : 0.156687 + py : 0.206868 + + 1 C s : -0.009402 s : -0.009402 + pz : -0.021208 p : -0.046468 + px : -0.014985 + py : -0.010275 + + 2 C s : 0.003454 s : 0.003454 + pz : 0.000982 p : 0.012339 + px : 0.009673 + py : 0.001685 + + 3 H s : 0.010220 s : 0.010220 + + 4 H s : -0.033860 s : -0.033860 + + 5 H s : -0.033578 s : -0.033578 + + 6 H s : 0.045785 s : 0.045785 + + 7 H s : -0.000819 s : -0.000819 + + 8 H s : -0.000612 s : -0.000612 + + 9 H s : -0.000776 s : -0.000776 + + + + ***************************** + * MAYER POPULATION ANALYSIS * + ***************************** + + NA - Mulliken gross atomic population + ZA - Total nuclear charge + QA - Mulliken gross atomic charge + VA - Mayer's total valence + BVA - Mayer's bonded valence + FA - Mayer's free valence + + ATOM NA ZA QA VA BVA FA + 0 C 6.1301 6.0000 -0.1301 3.9451 3.0311 0.9140 + 1 C 6.1389 6.0000 -0.1389 3.9610 3.9586 0.0023 + 2 C 6.2148 6.0000 -0.2148 3.9575 3.9573 0.0002 + 3 H 0.9270 1.0000 0.0730 0.9947 0.9945 0.0001 + 4 H 0.9389 1.0000 0.0611 0.9963 0.9941 0.0022 + 5 H 0.9397 1.0000 0.0603 0.9964 0.9942 0.0021 + 6 H 0.9274 1.0000 0.0726 0.9947 0.9923 0.0024 + 7 H 0.9268 1.0000 0.0732 0.9946 0.9946 0.0000 + 8 H 0.9280 1.0000 0.0720 0.9948 0.9948 0.0000 + 9 H 0.9283 1.0000 0.0717 0.9949 0.9949 0.0000 + + Mayer bond orders larger than 0.100000 +B( 0-C , 1-C ) : 1.0290 B( 0-C , 4-H ) : 0.9716 B( 0-C , 5-H ) : 0.9713 +B( 1-C , 2-C ) : 0.9941 B( 1-C , 3-H ) : 0.9658 B( 1-C , 6-H ) : 0.9490 +B( 2-C , 7-H ) : 0.9797 B( 2-C , 8-H ) : 0.9788 B( 2-C , 9-H ) : 0.9792 + + +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.872 sec +Sum of individual times .... 0.826 sec ( 94.7%) + +SCF preparation .... 0.241 sec ( 27.6%) +Fock matrix formation .... 0.523 sec ( 60.0%) + Startup .... 0.035 sec ( 6.7% of F) + Split-RI-J .... 0.027 sec ( 5.2% of F) + Chain of spheres X .... 0.318 sec ( 60.9% of F) + XC integration .... 0.127 sec ( 24.4% of F) + XC Preparation .... 0.000 sec ( 0.0% of XC) + Basis function eval. .... 0.032 sec ( 24.9% of XC) + Density eval. .... 0.010 sec ( 7.6% of XC) + XC-Functional eval. .... 0.028 sec ( 22.0% of XC) + XC-Potential eval. .... 0.008 sec ( 6.1% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.006 sec ( 0.7%) +Total Energy calculation .... 0.007 sec ( 0.8%) +Population analysis .... 0.018 sec ( 2.0%) +Orbital Transformation .... 0.005 sec ( 0.6%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.007 sec ( 0.8%) +SOSCF solution .... 0.019 sec ( 2.2%) +Finished LeanSCF after 0.9 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.0 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.958050385518 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + +----------------------------------------- + REACTANT (ANGSTROEM) +----------------------------------------- +C -1.332765 -0.020314 0.164762 +C 0.049224 0.473976 -0.241813 +C 1.287744 -0.381321 -0.009299 +H -1.503201 0.087467 1.254341 +H -1.458260 -1.087593 -0.081757 +H -2.123240 0.550757 -0.348950 +H 0.189824 1.556664 -0.371872 +H 1.624397 -0.338103 1.045523 +H 2.127413 -0.038519 -0.635704 +H 1.086496 -1.439306 -0.245326 + +----------------------------------------- + PRODUCT (ANGSTROEM) +----------------------------------------- +C 1.186849 0.291760 0.548240 +C 0.190459 -0.321200 -0.425264 +C -1.291135 0.008074 -0.060649 +H 0.326627 -1.417910 -0.453930 +H 2.189485 -0.139862 0.650206 +H 1.035271 1.316323 0.908179 +H 0.385916 0.044409 -1.456394 +H -1.543257 -0.385963 0.935731 +H -1.977258 -0.440165 -0.795961 +H -1.453658 1.096959 -0.052699 + + + +---------------------- +NEB settings +---------------------- +Method type .... climbing image +Threshold for climbing image .... 2.00e-02 Eh/Bohr +Free endpoints .... off +Tangent type .... improved +Number of intermediate images .... 15 +Number of images free to move .... 15 +Spring type for image distribution .... distance between adjacent images +Spring constant .... energy weighted (0.0100 -to- 0.1000) Eh/Bohr^2 +Spring force perp. to the path .... none +Generation of initial path .... image dependent pair potential +Initial path via TS guess .... off + +Minimization of RMSD: Rotation .... always +Minimization of RMSD: Translation type .... centroid +Center fixed to origin .... true +Remove external force .... true + +Reparametrization of the path .... off +Convergence thresholds: +Convergence monitored for .... all images +Scaling factor .... 10.00 + +Convergence parameters for regular images: + Max(|Fp|) .... 2.00e-02 Eh/Bohr + RMS(Fp) .... 1.00e-02 Eh/Bohr + +Convergence parameters for climbing image: + Max(|F|) .... 2.00e-03 Eh/Bohr + RMS(F) .... 1.00e-03 Eh/Bohr +Optimization method: +Method .... L-BFGS +Max. iterations .... 500 +Step size .... 1.00 +Maximum allowed step size .... 0.10 Bohr + +LBFGS parameters: + Memory .... 20 + Initial step size .... 0.0010 + Estimate curvature .... YES + Reset on maxmove .... YES + Reparam. on reset .... NO +Generation of the initial path: +Minimize RMSD between reactant and product configurations .... done + RMSD before minimization .... 3.3273 Bohr + RMSD after minimization .... 1.1600 Bohr +Performing linear interpolation .... done +Fragment preparation .... true +Bond cutoff factor .... 1.200e+00 +Max. fragment distance .... 3.500e+00 Ang. +Interpolation using .... IDPP (Image Dependent Pair Potential) +IDPP-Settings: + Initial path for IDPP optimization .... Linear interpolation + Pairwise distance interpolation .... Linear + Remove global transl. and rot. .... true + Convergence tolerance .... 0.0100 1/Ang.^3 + Max. number of iterations .... 7000 + Spring constant .... 1.0000 1/Ang.^4 + Time step .... 0.0100 fs + Max. movement per iteration .... 0.0500 Ang. + Full print .... false +idpp initial path generation successfully converged in 50 iterations +Displacement along initial path: 7.1643 Bohr +Writing initial trajectory to file .... input_initial_path_trj.xyz + + + +---------------------- +NEB OPTIMIZATION +---------------------- + +Following output files will be written: +Energy profile during opt. written to .... input.interp +Optimization log-file .... input.NEB.log +Current trajectory will be written to .... input_MEP_trj.xyz + and to allxyz file .... input_MEP.allxyz + and individual images to xyz file .... input_im{NIm}.xyz +Trajectory history will be written to .... input_MEP_ALL_trj.xyz +Converged CI will be written to .... input_NEB-CI_converged.xyz +Converged TS will be written to .... input_NEB-TS_converged.xyz + +Single point energy and gradient calculation of reactant and +product configurations (have to be performed only once) +Properties of fixed NEB end points: + Reactant: + E .... -116.966343 Eh + RMS(F) .... 0.000035 Eh/Bohr + MAX(|F|) .... 0.000096 Eh/Bohr + Product: + E .... -116.958049 Eh + RMS(F) .... 0.000041 Eh/Bohr + MAX(|F|) .... 0.000144 Eh/Bohr + + + +Starting iterations: + +Optim. Iteration HEI E(HEI)-E(0) max(|Fp|) RMS(Fp) dS +Switch-on CI threshold 0.020000 + LBFGS 0 7 0.180434 0.149847 0.027766 7.1643 +Warning: large step (max comp.: 0.541221 Bohr) was attempted. Maxmove condition invoked. + LBFGS 1 7 0.171350 0.120523 0.022508 7.1720 +Warning: large step (max comp.: 0.602483 Bohr) was attempted. Maxmove condition invoked. + LBFGS 2 7 0.159157 0.090457 0.018177 7.2318 +Warning: large step (max comp.: 0.436905 Bohr) was attempted. Maxmove condition invoked. + LBFGS 3 7 0.143466 0.062530 0.013798 7.3612 +Warning: large step (max comp.: 0.410838 Bohr) was attempted. Maxmove condition invoked. + LBFGS 4 7 0.126381 0.048937 0.010322 7.5601 +Warning: large step (max comp.: 0.407201 Bohr) was attempted. Maxmove condition invoked. + LBFGS 5 6 0.116726 0.037641 0.007948 7.7798 +Warning: large step (max comp.: 0.488717 Bohr) was attempted. Maxmove condition invoked. + LBFGS 6 6 0.110223 0.034362 0.006786 7.9925 +Warning: large step (max comp.: 0.111468 Bohr) was attempted. Maxmove condition invoked. + LBFGS 7 6 0.107417 0.053548 0.009628 8.2527 + LBFGS 8 6 0.105207 0.033976 0.006887 8.5371 +Warning: large step (max comp.: 0.266765 Bohr) was attempted. Maxmove condition invoked. + LBFGS 9 6 0.104797 0.028576 0.004545 8.8842 + LBFGS 10 6 0.104469 0.022364 0.003159 8.8894 + LBFGS 11 6 0.104362 0.023858 0.002980 8.9037 +Warning: large step (max comp.: 0.299037 Bohr) was attempted. Maxmove condition invoked. + LBFGS 12 6 0.104611 0.015494 0.002632 9.0715 + +Image 6 will be converted to a climbing image in the next iteration (max(|Fp|) < 0.0200) + +Optim. Iteration CI E(CI)-E(0) max(|Fp|) RMS(Fp) dS max(|FCI|) RMS(FCI) +Convergence thresholds 0.020000 0.010000 0.002000 0.001000 + LBFGS 13 6 0.104715 0.009622 0.001960 9.0772 0.042194 0.011494 + LBFGS 14 6 0.107018 0.044686 0.005487 9.1217 0.028883 0.008997 + LBFGS 15 6 0.107050 0.034378 0.004325 9.1343 0.026172 0.007804 +Warning: large step (max comp.: 0.182647 Bohr) was attempted. Maxmove condition invoked. + LBFGS 16 6 0.107733 0.011431 0.001918 9.3056 0.012829 0.004081 + LBFGS 17 6 0.107243 0.017593 0.002948 9.2892 0.011403 0.004099 + LBFGS 18 6 0.106971 0.012669 0.002167 9.3014 0.010553 0.003626 + LBFGS 19 6 0.106838 0.016187 0.002667 9.3307 0.011232 0.004308 +Warning: large step (max comp.: 0.116930 Bohr) was attempted. Maxmove condition invoked. + LBFGS 20 6 0.106471 0.026906 0.003870 9.4618 0.015161 0.005456 + LBFGS 21 6 0.105992 0.023886 0.003092 9.4457 0.008138 0.003145 + LBFGS 22 6 0.105843 0.011264 0.002006 9.4442 0.007819 0.002980 + LBFGS 23 6 0.105585 0.011651 0.001963 9.4723 0.005317 0.001743 + LBFGS 24 6 0.105494 0.011474 0.002111 9.4876 0.006913 0.002301 +Warning: large step (max comp.: 0.137022 Bohr) was attempted. Maxmove condition invoked. + LBFGS 25 6 0.105136 0.009845 0.002336 9.5287 0.007930 0.002434 + LBFGS 26 6 0.104874 0.021063 0.002854 9.4561 0.002497 0.001186 + LBFGS 27 6 0.104812 0.006007 0.001389 9.4331 0.002218 0.001241 + LBFGS 28 6 0.104753 0.009745 0.001455 9.4297 0.003496 0.001430 + LBFGS 29 6 0.104620 0.011450 0.001931 9.4421 0.003772 0.001458 + LBFGS 30 6 0.104209 0.021713 0.003167 9.5519 0.003406 0.001113 + LBFGS 31 6 0.103810 0.021131 0.003746 9.7678 0.004293 0.001562 +Warning: large step (max comp.: 0.162476 Bohr) was attempted. Maxmove condition invoked. + LBFGS 32 6 0.103500 0.020106 0.003539 10.0384 0.003702 0.001546 + LBFGS 33 6 0.103397 0.021179 0.003440 9.8680 0.002647 0.001096 + LBFGS 34 6 0.103364 0.017477 0.002306 9.8301 0.001565 0.000726 + + .--------------------. + ----------------------| CI-NEB convergence |------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS(Fp) 0.0023056034 0.0100000000 YES + MAX(|Fp|) 0.0174773805 0.0200000000 YES + RMS(FCI) 0.0007258778 0.0010000000 YES + MAX(|FCI|) 0.0015645135 0.0020000000 YES + --------------------------------------------------------------------- + +The elastic band and climbing image have converged successfully to a MEP in 34 iterations! + + + *********************H U R R A Y********************* + *** THE NEB OPTIMIZATION HAS CONVERGED *** + ***************************************************** + + + +--------------------------------------------------------------- + PATH SUMMARY +--------------------------------------------------------------- +All forces in Eh/Bohr. + +Image Dist.(Ang.) E(Eh) dE(kcal/mol) max(|Fp|) RMS(Fp) + 0 0.000 -116.96634 0.00 0.00010 0.00004 + 1 0.379 -116.96621 0.08 0.00051 0.00021 + 2 0.991 -116.96401 1.47 0.00286 0.00142 + 3 1.355 -116.93955 16.81 0.00748 0.00372 + 4 1.551 -116.90788 36.69 0.01748 0.00613 + 5 1.719 -116.87566 56.90 0.00912 0.00342 + 6 1.849 -116.86298 64.86 0.00139 0.00072 <= CI + 7 2.019 -116.88248 52.62 0.01092 0.00315 + 8 2.219 -116.91937 29.47 0.00538 0.00196 + 9 2.455 -116.94692 12.19 0.00341 0.00158 + 10 3.017 -116.95512 7.04 0.00381 0.00154 + 11 3.703 -116.95617 6.39 0.00210 0.00090 + 12 4.178 -116.95673 6.03 0.00106 0.00056 + 13 4.496 -116.95721 5.73 0.00058 0.00031 + 14 4.746 -116.95763 5.46 0.00035 0.00018 + 15 4.975 -116.95794 5.28 0.00017 0.00009 + 16 5.202 -116.95805 5.20 0.00014 0.00004 + +Straight line distance between images along the path: + D( 0- 1) = 0.3792 Ang. + D( 1- 2) = 0.6115 Ang. + D( 2- 3) = 0.3648 Ang. + D( 3- 4) = 0.1952 Ang. + D( 4- 5) = 0.1679 Ang. + D( 5- 6) = 0.1309 Ang. + D( 6- 7) = 0.1698 Ang. + D( 7- 8) = 0.2001 Ang. + D( 8- 9) = 0.2354 Ang. + D( 9-10) = 0.5621 Ang. + D(10-11) = 0.6865 Ang. + D(11-12) = 0.4745 Ang. + D(12-13) = 0.3184 Ang. + D(13-14) = 0.2494 Ang. + D(14-15) = 0.2294 Ang. + D(15-16) = 0.2268 Ang. + +--------------------------------------------------------------- + INFORMATION ABOUT SADDLE POINT +--------------------------------------------------------------- + +Climbing image .... 6 +Energy .... -116.86297980 Eh +Max. abs. force .... 1.5645e-03 Eh/Bohr + +----------------------------------------- + SADDLE POINT (ANGSTROEM) +----------------------------------------- +C -1.418476 -0.060465 0.002272 +C -0.021913 0.550356 -0.045914 +C 1.243473 -0.318881 -0.019816 +H -0.842487 0.646685 0.981788 +H -1.502985 -1.119285 0.256347 +H -2.222036 0.406717 -0.573499 +H 0.041176 1.524310 -0.543710 +H 1.439351 -0.747827 0.977821 +H 2.122621 0.278796 -0.304938 +H 1.161276 -1.160406 -0.730350 + +----------------------------------------- + FORCES (Eh/Bohr) +----------------------------------------- +C 0.000218 -0.000095 0.000785 +C 0.001156 0.000690 0.000526 +C -0.000686 -0.000041 0.000035 +H 0.001565 -0.000338 -0.001206 +H -0.000291 -0.000861 -0.000942 +H -0.001214 0.000244 0.001052 +H -0.000227 0.000205 -0.001364 +H -0.000956 -0.000223 0.000366 +H 0.000246 0.000604 0.000809 +H 0.000190 -0.000186 -0.000060 + +----------------------------------------- + UNIT TANGENT +----------------------------------------- +C -0.128312 -0.236932 -0.406986 +C -0.250407 0.061016 0.339694 +C -0.056392 0.009615 0.043982 +H 0.690710 0.254987 0.032377 +H -0.054152 -0.070375 -0.000136 +H -0.095239 -0.002637 -0.068134 +H -0.045817 -0.055174 0.032999 +H 0.005870 -0.005191 0.004220 +H -0.041089 0.014910 0.011367 +H -0.025172 0.029782 0.010617 + => Unit tangent is an approximation to the TS mode at the saddle point + +Next a TS optimization is performed on the CI from the NEB run. + + ************************************************************* + * TS OPTIMIZATION * + ************************************************************* + + +Following output files will be written: +Converged TS will be written to .... input_NEB-TS_converged.xyz + .... input.xyz +Current trajectory will be written to .... input_trj.xyz +Initial Hessian will be stored in .... input.appr.hess + (Almloef) Geometry optimization settings: +Update method Update .... Bofill +Choice of coordinates CoordSys .... (2022) Redundant Internals +Initial Hessian InHess .... Read +Max. no of cycles MaxIter .... 50 + +Convergence Tolerances: +Energy Change TolE .... 5.0000e-06 Eh +Max. Gradient TolMAXG .... 3.0000e-04 Eh/bohr +RMS Gradient TolRMSG .... 1.0000e-04 Eh/bohr +Max. Displacement TolMAXD .... 4.0000e-03 bohr +RMS Displacement TolRMSD .... 2.0000e-03 bohr +Strict Convergence .... False + +------------------------------------------------------------------------------ + ORCA OPTIMIZATION COORDINATE SETUP +------------------------------------------------------------------------------ + +The optimization will be done in redundant internal coordinates (2022) +Making redundant internal coordinates ... (2022 redundants) done +Following TS mode number ... 0 +TS-active-atoms for coordinate setup... 0 1 3 +Evaluating the initial hessian ... (Reading Exact Hessian)... +InHessName: input.appr.hess The file is opened as a .hess file +done +done +Evaluating the coordinates ... done +Calculating the B-matrix .... done +Calculating the G-matrix .... done +Diagonalizing the G-matrix .... done +The first mode is .... 21 +The number of degrees of freedom .... 24 + + ----------------------------------------------------------------- + Redundant Internal Coordinates + + + ----------------------------------------------------------------- + Definition Initial Value d2E/dq (diagonal element) + ----------------------------------------------------------------- + 1. B(C 1,C 0) 1.5251 0.246626 + 2. B(C 2,C 1) 1.5354 0.384567 + 3. B(H 3,C 0) 1.3384 0.031270 + 4. B(H 3,C 1) 1.3186 0.048874 + 5. B(H 4,C 0) 1.0922 0.361635 + 6. B(H 5,C 0) 1.0934 0.364594 + 7. B(H 6,C 1) 1.0956 0.355524 + 8. B(H 7,C 2) 1.1035 0.342812 + 9. B(H 8,C 2) 1.1006 0.346835 + 10. B(H 9,C 2) 1.1044 0.341661 + 11. A(C 1,C 0,H 3) 54.3667 0.007825 + 12. A(C 1,C 0,H 5) 119.0278 0.070166 + 13. A(H 3,C 0,H 4) 112.0414 0.050831 + 14. A(C 1,C 0,H 4) 117.8079 0.075773 + 15. A(H 4,C 0,H 5) 118.6776 0.117947 + 16. A(H 3,C 0,H 5) 118.4196 0.045504 + 17. A(C 0,C 1,H 3) 55.5821 0.001041 + 18. A(H 3,C 1,H 6) 108.9657 0.059129 + 19. A(C 2,C 1,H 6) 117.6153 0.121954 + 20. A(C 0,C 1,H 6) 115.0326 0.073987 + 21. A(C 0,C 1,C 2) 121.8310 0.057641 + 22. A(C 2,C 1,H 3) 122.7494 0.032279 + 23. A(C 1,C 2,H 8) 110.2711 0.251495 + 24. A(C 1,C 2,H 7) 112.4409 0.252300 + 25. A(H 7,C 2,H 9) 107.3775 0.209770 + 26. A(C 1,C 2,H 9) 111.0444 0.218572 + 27. A(H 7,C 2,H 8) 107.6682 0.114703 + 28. A(H 8,C 2,H 9) 107.8513 0.214431 + 29. A(C 0,H 3,C 1) 70.0512 0.057253 + 30. D(H 3,C 1,C 0,H 5) 105.7773 0.025744 + 31. D(C 2,C 1,C 0,H 4) 11.9969 0.021582 + 32. D(H 6,C 1,C 0,H 3) -96.5944 0.027163 + 33. D(C 2,C 1,C 0,H 5) -143.9489 0.020518 + 34. D(H 3,C 1,C 0,H 4) -98.2769 0.026253 + 35. D(C 2,C 1,C 0,H 3) 110.2738 0.020191 + 36. D(H 7,C 2,C 1,C 0) -73.4996 0.016431 + 37. D(H 8,C 2,C 1,H 6) 13.8538 0.017253 + 38. D(H 8,C 2,C 1,H 3) -126.7331 0.017269 + 39. D(H 8,C 2,C 1,C 0) 166.3289 0.016100 + 40. D(H 7,C 2,C 1,H 6) 134.0253 0.017556 + 41. D(H 7,C 2,C 1,H 3) -6.5615 0.019087 + 42. D(C 0,H 3,C 1,C 2) -108.6306 0.050545 + 43. D(C 1,H 3,C 0,H 5) -106.9138 0.059592 + 44. D(C 1,H 3,C 0,H 4) 109.2095 0.057230 + 45. D(C 0,H 3,C 1,H 6) 107.8729 0.045248 + ----------------------------------------------------------------- + +Number of atoms .... 10 +Number of degrees of freedom .... 45 + + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 1 * + ************************************************************* + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1108 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.720568990033 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.246e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40955 +Total number of batches ... 646 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4096 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5309 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 531 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10985 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24093 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2409 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 74.7205689900 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8629875828599012 0.00e+00 2.75e-07 1.58e-06 4.31e-07 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8629875828797964 -1.99e-11 1.94e-07 1.27e-06 6.23e-07 0.1 + *** Gradient check signals convergence *** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 2 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.101 sec) +Old exchange energy : -3.604411622 Eh +New exchange energy : -3.604403842 Eh +Exchange energy change after final integration : 0.000007780 Eh +Total energy after final integration : -116.862979803 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86297980309321 Eh -3180.00335 eV + +Components: +Nuclear Repulsion : 74.72056899003307 Eh 2033.25005 eV +Electronic Energy : -191.58355657291287 Eh -5213.25361 eV +One Electron Energy: -304.48800888914843 Eh -8285.53995 eV +Two Electron Energy: 112.90445231623558 Eh 3072.28634 eV + +Virial components: +Potential Energy : -232.18073371246345 Eh -6317.95896 eV +Kinetic Energy : 115.31775390937023 Eh 3137.95561 eV +Virial Ratio : 2.01339972243075 + +DFT components: +N(Alpha) : 13.000000100975 electrons +N(Beta) : 11.999999794602 electrons +N(Total) : 24.999999895577 electrons +E(X) : -14.252377251274 Eh +E(C) : -0.919709511981 Eh +E(XC) : -15.172086763255 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9895e-11 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2735e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9363e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 5.3420e-07 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.2321e-07 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.9462e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762641 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012641 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.002761 -272.1890 + 1 1.0000 -9.979719 -271.5620 + 2 1.0000 -9.965559 -271.1767 + 3 1.0000 -0.740970 -20.1628 + 4 1.0000 -0.645910 -17.5761 + 5 1.0000 -0.521185 -14.1822 + 6 1.0000 -0.424359 -11.5474 + 7 1.0000 -0.388411 -10.5692 + 8 1.0000 -0.365686 -9.9508 + 9 1.0000 -0.345096 -9.3905 + 10 1.0000 -0.306397 -8.3375 + 11 1.0000 -0.251767 -6.8509 + 12 1.0000 -0.059853 -1.6287 + 13 0.0000 0.298490 8.1223 + 14 0.0000 0.372558 10.1378 + 15 0.0000 0.398027 10.8309 + 16 0.0000 0.419364 11.4115 + 17 0.0000 0.461224 12.5505 + 18 0.0000 0.475618 12.9422 + 19 0.0000 0.487845 13.2749 + 20 0.0000 0.534566 14.5463 + 21 0.0000 0.594353 16.1732 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.003020 -272.1960 + 1 1.0000 -9.970531 -271.3119 + 2 1.0000 -9.955741 -270.9095 + 3 1.0000 -0.720995 -19.6193 + 4 1.0000 -0.635955 -17.3052 + 5 1.0000 -0.501158 -13.6372 + 6 1.0000 -0.412825 -11.2335 + 7 1.0000 -0.377555 -10.2738 + 8 1.0000 -0.360360 -9.8059 + 9 1.0000 -0.340005 -9.2520 + 10 1.0000 -0.300631 -8.1806 + 11 1.0000 -0.224391 -6.1060 + 12 0.0000 0.095827 2.6076 + 13 0.0000 0.321581 8.7507 + 14 0.0000 0.386758 10.5242 + 15 0.0000 0.413065 11.2401 + 16 0.0000 0.433157 11.7868 + 17 0.0000 0.473782 12.8923 + 18 0.0000 0.483471 13.1559 + 19 0.0000 0.491320 13.3695 + 20 0.0000 0.546808 14.8794 + 21 0.0000 0.608024 16.5452 +*Only the first 10 virtual orbitals were printed. +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.577 sec +Sum of individual times .... 0.557 sec ( 96.4%) + +SCF preparation .... 0.200 sec ( 34.7%) +Fock matrix formation .... 0.323 sec ( 56.0%) + Startup .... 0.005 sec ( 1.5% of F) + Split-RI-J .... 0.014 sec ( 4.2% of F) + Chain of spheres X .... 0.220 sec ( 67.9% of F) + XC integration .... 0.078 sec ( 24.1% of F) + Basis function eval. .... 0.017 sec ( 22.3% of XC) + Density eval. .... 0.005 sec ( 6.8% of XC) + XC-Functional eval. .... 0.015 sec ( 19.4% of XC) + XC-Potential eval. .... 0.005 sec ( 6.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.003 sec ( 0.6%) +Total Energy calculation .... 0.005 sec ( 0.8%) +Population analysis .... 0.000 sec ( 0.0%) +Orbital Transformation .... 0.006 sec ( 1.0%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.008 sec ( 1.4%) +SOSCF solution .... 0.011 sec ( 2.0%) +Finished LeanSCF after 0.6 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.5 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.862979803093 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000219107 0.000094545 -0.000785518 + 2 C : -0.001156688 -0.000688409 -0.000525015 + 3 C : 0.000687259 0.000039767 -0.000034475 + 4 H : -0.001563439 0.000337768 0.001205637 + 5 H : 0.000291500 0.000860765 0.000942472 + 6 H : 0.001213844 -0.000244594 -0.001051670 + 7 H : 0.000226608 -0.000205347 0.001363653 + 8 H : 0.000956382 0.000222879 -0.000366654 + 9 H : -0.000246016 -0.000603613 -0.000808747 + 10 H : -0.000190344 0.000186238 0.000060316 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000429564 0.0000743695 0.0000881537 + +Norm of the Cartesian gradient ... 0.0039758378 +RMS gradient ... 0.0007258853 +MAX gradient ... 0.0015634390 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.656 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.115 sec ( 17.6%) +COSX gradient .... 0.413 sec ( 63.0%) +XC gradient .... 0.122 sec ( 18.6%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.862979803 Eh +Current gradient norm .... 0.003975838 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Evaluating the initial hessian .... (read) +(Reading Exact Hessian)... +InHessName: input.appr.hess The file is opened as a .hess file +done +done +Projecting the Hessian .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124610005 0.005067728 0.029216093 0.043012026 0.052656094 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12461001 and components: + 1. 0.00338856 + 2. 0.04846114 + 3. 0.55535050 + 4. -0.51896923 + 5. -0.01021737 + 6. -0.01344442 + 7. -0.00018539 + 8. -0.00678875 + 9. 0.00153627 + 10. -0.00816328 + 11. -0.29879331 + 12. 0.01827949 + 13. 0.00372424 + 14. -0.00950039 + 15. 0.07007021 + 16. 0.01741594 + 17. 0.31184142 + 18. 0.03251562 + 19. -0.04632839 + 20. 0.03163984 + 21. -0.06061174 + 22. -0.09282473 + 23. 0.00534658 + 24. -0.02183750 + 25. 0.00856256 + 26. 0.01355100 + 27. 0.00227670 + 28. -0.00776649 + 29. -0.01304811 + 30. -0.10014319 + 31. 0.15615433 + 32. -0.14319907 + 33. -0.06107363 + 34. 0.11708476 + 35. 0.03906956 + 36. -0.16789463 + 37. 0.00723293 + 38. 0.16780281 + 39. -0.15991841 + 40. -0.00074329 + 41. 0.15982660 + 42. -0.10829964 + 43. 0.09068192 + 44. -0.06759339 + 45. 0.06250518 + +Lambda that maximizes along the TS mode: 0.00000736 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00047034 step = 0.00047034 +In cycle 2: lambdaN = -0.00047248 step = 0.00000213 +In cycle 3: lambdaN = -0.00047248 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00047248 +Calculated stepsize too large ( 0.2265 > 0.1000). Scaled with 0.4414. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0203225629 RMS(Int)= 0.0148934787 +done +Storing new coordinates .... done + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + RMS gradient 0.0006663973 0.0001000000 NO + MAX gradient 0.0015548504 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0419885479 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0020 Max(Angles) 0.30 + Max(Dihed) 2.41 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5251 -0.000876 0.0006 1.5257 + 2. B(C 2,C 1) 1.5354 0.001067 -0.0006 1.5348 + 3. B(H 3,C 0) 1.3384 -0.000198 -0.0020 1.3364 0.56 + 4. B(H 3,C 1) 1.3186 0.001423 -0.0004 1.3183 0.52 + 5. B(H 4,C 0) 1.0922 -0.000641 0.0004 1.0925 + 6. B(H 5,C 0) 1.0934 -0.000441 0.0002 1.0936 + 7. B(H 6,C 1) 1.0956 -0.000789 0.0006 1.0962 + 8. B(H 7,C 2) 1.1035 -0.000245 0.0002 1.1036 + 9. B(H 8,C 2) 1.1006 -0.000317 0.0002 1.1009 + 10. B(H 9,C 2) 1.1044 -0.000166 0.0002 1.1046 + 11. A(C 1,C 0,H 3) 54.37 0.000835 -0.00 54.36 0.30 + 12. A(C 1,C 0,H 5) 119.03 -0.000746 0.20 119.22 + 13. A(H 3,C 0,H 4) 112.04 -0.000486 0.18 112.22 + 14. A(C 1,C 0,H 4) 117.81 -0.000125 -0.05 117.75 + 15. A(H 4,C 0,H 5) 118.68 0.000621 -0.05 118.63 + 16. A(H 3,C 0,H 5) 118.42 -0.000060 -0.30 118.12 + 17. A(C 0,C 1,H 3) 55.58 -0.000074 -0.10 55.48 0.31 + 18. A(H 3,C 1,H 6) 108.97 -0.000490 0.27 109.24 + 19. A(C 2,C 1,H 6) 117.62 -0.000547 0.09 117.70 + 20. A(C 0,C 1,H 6) 115.03 -0.000065 -0.08 114.95 + 21. A(C 0,C 1,C 2) 121.83 0.000563 -0.00 121.83 + 22. A(C 2,C 1,H 3) 122.75 0.000933 -0.27 122.48 + 23. A(C 1,C 2,H 8) 110.27 0.000175 -0.03 110.24 + 24. A(C 1,C 2,H 7) 112.44 0.001310 -0.12 112.32 + 25. A(H 7,C 2,H 9) 107.38 -0.000226 0.05 107.43 + 26. A(C 1,C 2,H 9) 111.04 -0.000660 0.09 111.13 + 27. A(H 7,C 2,H 8) 107.67 -0.000486 -0.03 107.64 + 28. A(H 8,C 2,H 9) 107.85 -0.000172 0.05 107.90 + 29. A(C 0,H 3,C 1) 70.05 -0.000761 0.10 70.16 + 30. D(H 3,C 1,C 0,H 5) 105.78 0.000674 -0.50 105.28 + 31. D(C 2,C 1,C 0,H 4) 12.00 0.001075 -0.66 11.34 + 32. D(H 6,C 1,C 0,H 3) -96.59 0.000612 -0.36 -96.96 + 33. D(C 2,C 1,C 0,H 5) -143.95 0.001555 -0.89 -144.84 + 34. D(H 3,C 1,C 0,H 4) -98.28 0.000194 -0.27 -98.55 + 35. D(C 2,C 1,C 0,H 3) 110.27 0.000881 -0.39 109.89 + 36. D(H 7,C 2,C 1,C 0) -73.50 -0.000549 2.24 -71.26 + 37. D(H 8,C 2,C 1,H 6) 13.85 -0.000783 2.41 16.26 + 38. D(H 8,C 2,C 1,H 3) -126.73 -0.000400 2.15 -124.59 + 39. D(H 8,C 2,C 1,C 0) 166.33 -0.000926 2.38 168.71 + 40. D(H 7,C 2,C 1,H 6) 134.03 -0.000405 2.27 136.29 + 41. D(H 7,C 2,C 1,H 3) -6.56 -0.000023 2.01 -4.56 + 42. D(C 0,H 3,C 1,C 2) -108.63 -0.000223 -0.09 -108.72 + 43. D(C 1,H 3,C 0,H 5) -106.91 0.000628 -0.43 -107.34 + 44. D(C 1,H 3,C 0,H 4) 109.21 0.000295 -0.18 109.03 + 45. D(C 0,H 3,C 1,H 6) 107.87 0.000209 -0.28 107.59 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s ( 1.657 %) +Internal coordinates : 0.000 s ( 0.344 %) +B/P matrices and projection : 0.000 s ( 2.460 %) +Hessian update/contruction : 0.015 s (86.970 %) +Making the step : 0.001 s ( 3.189 %) +Converting the step to Cartesian: 0.000 s ( 0.442 %) +Storing new data : 0.000 s ( 0.298 %) +Checking convergence : 0.000 s ( 0.017 %) +Final printing : 0.001 s ( 4.605 %) +Total time : 0.017 s + +Time for energy+gradient : 5.218 s +Time for complete geometry iter : 6.093 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 2 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.418284 -0.059858 0.007851 + C -0.021067 0.549782 -0.054292 + C 1.243459 -0.319392 -0.020723 + H -0.836258 0.653616 0.976483 + H -1.500583 -1.118073 0.266640 + H -2.229610 0.405654 -0.558674 + H 0.038934 1.517227 -0.566265 + H 1.419229 -0.765362 0.973371 + H 2.127685 0.284511 -0.276437 + H 1.176495 -1.148106 -0.747954 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.680169 -0.113114 0.014836 + 1 C 6.0000 0 12.011 -0.039811 1.038937 -0.102597 + 2 C 6.0000 0 12.011 2.349797 -0.603564 -0.039162 + 3 H 1.0000 0 1.008 -1.580299 1.235155 1.845285 + 4 H 1.0000 0 1.008 -2.835690 -2.112851 0.503877 + 5 H 1.0000 0 1.008 -4.213352 0.766575 -1.055740 + 6 H 1.0000 0 1.008 0.073574 2.867144 -1.070085 + 7 H 1.0000 0 1.008 2.681954 -1.446325 1.839405 + 8 H 1.0000 0 1.008 4.020742 0.537649 -0.522390 + 9 H 1.0000 0 1.008 2.223254 -2.169606 -1.413429 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.525692523297 0.00000000 0.00000000 + C 2 1 0 1.534801556634 121.82620951 0.00000000 + H 2 1 3 1.318261782839 55.48059909 250.11151148 + H 1 2 3 1.092503581790 117.75397760 11.34011362 + H 1 2 3 1.093572162599 119.22465713 215.16360009 + H 2 1 3 1.096205753267 114.94803559 153.15377692 + H 3 2 1 1.103634350351 112.31885700 288.74353763 + H 3 2 1 1.100883831522 110.24397753 168.71238248 + H 3 2 1 1.104588332848 111.13247347 49.12692084 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.883141033603 0.00000000 0.00000000 + C 2 1 0 2.900354611955 121.82620951 0.00000000 + H 2 1 3 2.491153742380 55.48059909 250.11151148 + H 1 2 3 2.064532569910 117.75397760 11.34011362 + H 1 2 3 2.066551894993 119.22465713 215.16360009 + H 2 1 3 2.071528660103 114.94803559 153.15377692 + H 3 2 1 2.085566674151 112.31885700 288.74353763 + H 3 2 1 2.080368946839 110.24397753 168.71238248 + H 3 2 1 2.087369439807 111.13247347 49.12692084 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1108 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.719540071838 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.246e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40952 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5307 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 531 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10983 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24083 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8629709775162837 0.00e+00 7.39e-04 5.41e-03 7.33e-04 0.2 + *** Restarting incremental Fock matrix formation *** + 2 -116.8631545531122811 -1.84e-04 3.86e-04 2.25e-03 9.54e-04 0.1 + 3 -116.8631804308016058 -2.59e-05 8.54e-05 4.54e-04 2.64e-04 0.1 + 4 -116.8631812066203395 -7.76e-07 3.39e-05 2.17e-04 8.76e-05 0.1 + 5 -116.8631812264540599 -1.98e-08 1.27e-05 6.91e-05 5.96e-05 0.1 + 6 -116.8631812639346492 -3.75e-08 2.84e-06 1.95e-05 5.20e-06 0.1 + 7 -116.8631812654072064 -1.47e-09 1.68e-06 1.36e-05 2.54e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.100 sec) +Old exchange energy : -3.604351779 Eh +New exchange energy : -3.604349027 Eh +Exchange energy change after final integration : 0.000002751 Eh +Total energy after final integration : -116.863178514 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86317851400540 Eh -3180.00876 eV + +Components: +Nuclear Repulsion : 74.71954007183837 Eh 2033.22205 eV +Electronic Energy : -191.58272133724557 Eh -5213.23088 eV +One Electron Energy: -304.48582199820783 Eh -8285.48044 eV +Two Electron Energy: 112.90310066096225 Eh 3072.24956 eV + +Virial components: +Potential Energy : -232.17963779511771 Eh -6317.92914 eV +Kinetic Energy : 115.31645928111232 Eh 3137.92039 eV +Virial Ratio : 2.01341282278814 + +DFT components: +N(Alpha) : 13.000000464554 electrons +N(Beta) : 12.000000272650 electrons +N(Total) : 25.000000737204 electrons +E(X) : -14.252172993876 Eh +E(C) : -0.919702877114 Eh +E(XC) : -15.171875870991 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.4726e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3592e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6840e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0158e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.5410e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.2044e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762577 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012577 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.6 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.863178514005 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000448630 0.000723490 -0.001237894 + 2 C : -0.000764210 -0.001253257 0.000529491 + 3 C : 0.000441307 -0.000284705 -0.000252773 + 4 H : -0.001042960 0.000318274 0.000747676 + 5 H : 0.000412506 0.000568625 0.000844529 + 6 H : 0.000674280 -0.000296661 -0.000874126 + 7 H : -0.000000263 0.000123092 0.001000268 + 8 H : 0.001059793 0.000319832 -0.000103891 + 9 H : -0.000128600 -0.000393571 -0.000723142 + 10 H : -0.000203223 0.000174881 0.000069863 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000370653 0.0000779221 0.0000637921 + +Norm of the Cartesian gradient ... 0.0035094811 +RMS gradient ... 0.0006407406 +MAX gradient ... 0.0012532566 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.672 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 17.4%) +COSX gradient .... 0.423 sec ( 62.9%) +XC gradient .... 0.127 sec ( 18.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.863178514 Eh +Current gradient norm .... 0.003509481 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124627036 0.000218588 0.028086062 0.042160270 0.052644347 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12462704 and components: + 1. -0.00324333 + 2. -0.04877417 + 3. -0.55538254 + 4. 0.51877096 + 5. 0.01022785 + 6. 0.01337287 + 7. 0.00013169 + 8. 0.00671909 + 9. -0.00155055 + 10. 0.00822156 + 11. 0.29867935 + 12. -0.01830271 + 13. -0.00344487 + 14. 0.00969823 + 15. -0.07015469 + 16. -0.01770495 + 17. -0.31186231 + 18. -0.03211731 + 19. 0.04652243 + 20. -0.03133541 + 21. 0.06019838 + 22. 0.09222862 + 23. -0.00529472 + 24. 0.02139624 + 25. -0.00852319 + 26. -0.01335888 + 27. -0.00208389 + 28. 0.00774425 + 29. 0.01318296 + 30. 0.09973817 + 31. -0.15690689 + 32. 0.14289178 + 33. 0.06010199 + 34. -0.11727071 + 35. -0.03963618 + 36. 0.16913036 + 37. -0.00627397 + 38. -0.16700034 + 39. 0.16116527 + 40. 0.00169112 + 41. -0.15903526 + 42. 0.10853483 + 43. -0.09077925 + 44. 0.06764647 + 45. -0.06238401 + +Lambda that maximizes along the TS mode: 0.00000193 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00021702 step = 0.00021702 +In cycle 2: lambdaN = -0.00061890 step = 0.00040188 +In cycle 3: lambdaN = -0.00118772 step = 0.00056882 +In cycle 4: lambdaN = -0.00156629 step = 0.00037857 +In cycle 5: lambdaN = -0.00162647 step = 0.00006018 +In cycle 6: lambdaN = -0.00162741 step = 0.00000094 +In cycle 7: lambdaN = -0.00162741 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00162741 +Calculated stepsize too large ( 0.7551 > 0.1000). Scaled with 0.1324. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0203582130 RMS(Int)= 0.0148844785 +done +Storing new coordinates .... done +The predicted energy change is .... 0.005936457 +Previously predicted energy change .... -0.000162359 +Actually observed energy change .... -0.000198711 +Ratio of predicted to observed change .... 1.223895840 +New trust radius .... 0.150000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001987109 0.0000050000 NO + RMS gradient 0.0005595245 0.0001000000 NO + MAX gradient 0.0012863357 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0397322080 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.31 + Max(Dihed) 2.28 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5257 -0.000630 0.0005 1.5262 + 2. B(C 2,C 1) 1.5348 0.001048 -0.0008 1.5340 + 3. B(H 3,C 0) 1.3364 -0.000114 -0.0005 1.3359 0.56 + 4. B(H 3,C 1) 1.3183 0.000900 -0.0007 1.3175 0.52 + 5. B(H 4,C 0) 1.0925 -0.000384 0.0000 1.0925 + 6. B(H 5,C 0) 1.0936 -0.000172 -0.0002 1.0933 + 7. B(H 6,C 1) 1.0962 -0.000358 -0.0000 1.0962 + 8. B(H 7,C 2) 1.1036 -0.000051 -0.0002 1.1035 + 9. B(H 8,C 2) 1.1009 -0.000153 0.0000 1.1009 + 10. B(H 9,C 2) 1.1046 -0.000165 0.0002 1.1048 + 11. A(C 1,C 0,H 3) 54.36 0.000545 -0.04 54.33 0.30 + 12. A(C 1,C 0,H 5) 119.22 -0.000357 0.07 119.29 + 13. A(H 3,C 0,H 4) 112.22 -0.000463 0.18 112.40 + 14. A(C 1,C 0,H 4) 117.75 -0.000283 0.03 117.79 + 15. A(H 4,C 0,H 5) 118.63 0.000472 -0.02 118.61 + 16. A(H 3,C 0,H 5) 118.12 0.000067 -0.27 117.85 + 17. A(C 0,C 1,H 3) 55.48 -0.000022 -0.03 55.45 0.31 + 18. A(H 3,C 1,H 6) 109.24 -0.000520 0.28 109.52 + 19. A(C 2,C 1,H 6) 117.70 -0.000465 0.08 117.78 + 20. A(C 0,C 1,H 6) 114.95 -0.000300 0.04 114.99 + 21. A(C 0,C 1,C 2) 121.83 0.000697 -0.12 121.71 + 22. A(C 2,C 1,H 3) 122.48 0.000891 -0.31 122.17 + 23. A(C 1,C 2,H 8) 110.24 0.000036 0.01 110.25 + 24. A(C 1,C 2,H 7) 112.32 0.001242 -0.16 112.16 + 25. A(H 7,C 2,H 9) 107.43 -0.000165 0.03 107.46 + 26. A(C 1,C 2,H 9) 111.13 -0.000584 0.09 111.22 + 27. A(H 7,C 2,H 8) 107.64 -0.000505 0.02 107.66 + 28. A(H 8,C 2,H 9) 107.90 -0.000072 0.01 107.91 + 29. A(C 0,H 3,C 1) 70.16 -0.000523 0.06 70.22 + 30. D(H 3,C 1,C 0,H 5) 105.28 0.000507 -0.40 104.87 + 31. D(C 2,C 1,C 0,H 4) 11.34 0.000969 -0.54 10.80 + 32. D(H 6,C 1,C 0,H 3) -96.96 0.000480 -0.33 -97.29 + 33. D(C 2,C 1,C 0,H 5) -144.84 0.001286 -0.75 -145.59 + 34. D(H 3,C 1,C 0,H 4) -98.55 0.000189 -0.19 -98.74 + 35. D(C 2,C 1,C 0,H 3) 109.89 0.000780 -0.35 109.54 + 36. D(H 7,C 2,C 1,C 0) -71.26 -0.000720 2.28 -68.98 + 37. D(H 8,C 2,C 1,H 6) 16.26 -0.000674 2.28 18.54 + 38. D(H 8,C 2,C 1,H 3) -124.59 -0.000301 2.28 -122.31 + 39. D(H 8,C 2,C 1,C 0) 168.71 -0.000928 2.28 170.99 + 40. D(H 7,C 2,C 1,H 6) 136.29 -0.000465 2.28 138.57 + 41. D(H 7,C 2,C 1,H 3) -4.56 -0.000093 2.28 -2.28 + 42. D(C 0,H 3,C 1,C 2) -108.72 -0.000434 0.01 -108.71 + 43. D(C 1,H 3,C 0,H 5) -107.34 0.000312 -0.23 -107.57 + 44. D(C 1,H 3,C 0,H 4) 109.03 0.000035 -0.08 108.95 + 45. D(C 0,H 3,C 1,H 6) 107.59 -0.000052 -0.13 107.46 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (10.782 %) +Internal coordinates : 0.000 s ( 1.527 %) +B/P matrices and projection : 0.000 s (13.995 %) +Hessian update/contruction : 0.001 s (24.682 %) +Making the step : 0.001 s (18.830 %) +Converting the step to Cartesian: 0.000 s ( 2.163 %) +Storing new data : 0.000 s ( 1.559 %) +Checking convergence : 0.000 s ( 0.636 %) +Final printing : 0.001 s (25.732 %) +Total time : 0.003 s + +Time for energy+gradient : 5.885 s +Time for complete geometry iter : 6.707 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 3 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.417441 -0.060178 0.013551 + C -0.020729 0.549728 -0.062583 + C 1.242709 -0.319330 -0.021750 + H -0.828862 0.661812 0.971727 + H -1.497952 -1.117010 0.278621 + H -2.234705 0.403056 -0.545831 + H 0.037060 1.510354 -0.587471 + H 1.397210 -0.783276 0.967457 + H 2.131603 0.289424 -0.248180 + H 1.191107 -1.134580 -0.765542 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.678576 -0.113720 0.025608 + 1 C 6.0000 0 12.011 -0.039173 1.038836 -0.118265 + 2 C 6.0000 0 12.011 2.348380 -0.603446 -0.041101 + 3 H 1.0000 0 1.008 -1.566321 1.250644 1.836298 + 4 H 1.0000 0 1.008 -2.830718 -2.110842 0.526517 + 5 H 1.0000 0 1.008 -4.222980 0.761666 -1.031472 + 6 H 1.0000 0 1.008 0.070033 2.854155 -1.110159 + 7 H 1.0000 0 1.008 2.640344 -1.480178 1.828229 + 8 H 1.0000 0 1.008 4.028146 0.546932 -0.468992 + 9 H 1.0000 0 1.008 2.250866 -2.144046 -1.446664 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.525970925338 0.00000000 0.00000000 + C 2 1 0 1.534016485124 121.74168425 0.00000000 + H 2 1 3 1.317359954458 55.48291669 250.45377784 + H 1 2 3 1.092536943587 117.78634294 10.80607833 + H 1 2 3 1.093349834462 119.29482483 214.41290768 + H 2 1 3 1.096196841492 114.98591972 153.19429935 + H 3 2 1 1.103470556792 112.17089631 291.07133658 + H 3 2 1 1.100901422502 110.25907973 171.06365220 + H 3 2 1 1.104772242733 111.20266376 51.42557515 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.883667137216 0.00000000 0.00000000 + C 2 1 0 2.898871041804 121.74168425 0.00000000 + H 2 1 3 2.489449533721 55.48291669 250.45377784 + H 1 2 3 2.064595614570 117.78634294 10.80607833 + H 1 2 3 2.066131755701 119.29482483 214.41290768 + H 2 1 3 2.071511819290 114.98591972 153.19429935 + H 3 2 1 2.085257149183 112.17089631 291.07133658 + H 3 2 1 2.080402188973 110.25907973 171.06365220 + H 3 2 1 2.087716979124 111.20266376 51.42557515 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.735853943618 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.245e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40956 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4096 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5303 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10984 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24081 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2408 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8631510196769909 0.00e+00 7.36e-04 5.52e-03 7.57e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8633344825340714 -1.83e-04 3.74e-04 2.29e-03 9.93e-04 0.1 + 3 -116.8633594979247050 -2.50e-05 7.28e-05 4.21e-04 1.48e-04 0.1 + 4 -116.8633601060429044 -6.08e-07 8.66e-06 4.99e-05 2.20e-05 0.1 + 5 -116.8633601171088685 -1.11e-08 3.19e-06 2.10e-05 9.19e-06 0.1 + 6 -116.8633601171108580 -1.99e-12 1.63e-06 1.30e-05 8.74e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.103 sec) +Old exchange energy : -3.604409093 Eh +New exchange energy : -3.604411869 Eh +Exchange energy change after final integration : -0.000002776 Eh +Total energy after final integration : -116.863362893 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86336289323329 Eh -3180.01377 eV + +Components: +Nuclear Repulsion : 74.73585394361822 Eh 2033.66598 eV +Electronic Energy : -191.59921406072908 Eh -5213.67967 eV +One Electron Energy: -304.51714433182957 Eh -8286.33277 eV +Two Electron Energy: 112.91793027110049 Eh 3072.65309 eV + +Virial components: +Potential Energy : -232.18007125964067 Eh -6317.94094 eV +Kinetic Energy : 115.31670836640737 Eh 3137.92716 eV +Virial Ratio : 2.01341223270015 + +DFT components: +N(Alpha) : 13.000001900058 electrons +N(Beta) : 12.000001811071 electrons +N(Total) : 25.000003711129 electrons +E(X) : -14.252349757820 Eh +E(C) : -0.919725650507 Eh +E(XC) : -15.172075408327 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9895e-12 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2956e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.6273e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0406e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 8.7424e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3187e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762540 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012540 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.7 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.863362893233 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000361294 0.001143404 -0.001131819 + 2 C : -0.000163557 -0.001336668 0.000450341 + 3 C : 0.000274444 -0.000365481 -0.000258862 + 4 H : -0.001358552 0.000094598 0.000583364 + 5 H : 0.000431509 0.000514339 0.000737834 + 6 H : 0.000579653 -0.000376953 -0.000629190 + 7 H : -0.000047773 0.000087848 0.000957716 + 8 H : 0.000973011 0.000420286 -0.000052142 + 9 H : -0.000164548 -0.000319191 -0.000733196 + 10 H : -0.000162893 0.000137818 0.000075952 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000355530 0.0000703830 0.0000396098 + +Norm of the Cartesian gradient ... 0.0034418403 +RMS gradient ... 0.0006283912 +MAX gradient ... 0.0013585517 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.662 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.116 sec ( 17.6%) +COSX gradient .... 0.413 sec ( 62.4%) +XC gradient .... 0.127 sec ( 19.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.863362893 Eh +Current gradient norm .... 0.003441840 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.150 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124713637 0.000156326 0.028027482 0.042215910 0.052648669 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12471364 and components: + 1. -0.00331761 + 2. -0.04854489 + 3. -0.55521960 + 4. 0.51888624 + 5. 0.01021965 + 6. 0.01339535 + 7. 0.00011610 + 8. 0.00676071 + 9. -0.00156258 + 10. 0.00815135 + 11. 0.29872229 + 12. -0.01840680 + 13. -0.00410990 + 14. 0.00951804 + 15. -0.07008331 + 16. -0.01678166 + 17. -0.31179063 + 18. -0.03297692 + 19. 0.04629440 + 20. -0.03151757 + 21. 0.06054280 + 22. 0.09325579 + 23. -0.00541186 + 24. 0.02182319 + 25. -0.00855799 + 26. -0.01351866 + 27. -0.00225179 + 28. 0.00778677 + 29. 0.01306834 + 30. 0.10101161 + 31. -0.15500436 + 32. 0.14384152 + 33. 0.06254605 + 34. -0.11653879 + 35. -0.03846556 + 36. 0.16062431 + 37. -0.01455951 + 38. -0.17484793 + 39. 0.15267046 + 40. -0.00660566 + 41. -0.16689408 + 42. 0.10858511 + 43. -0.09011806 + 44. 0.06784233 + 45. -0.06207281 + +Lambda that maximizes along the TS mode: 0.00000601 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00015577 step = 0.00015577 +In cycle 2: lambdaN = -0.00045510 step = 0.00029933 +In cycle 3: lambdaN = -0.00095047 step = 0.00049537 +In cycle 4: lambdaN = -0.00145373 step = 0.00050326 +In cycle 5: lambdaN = -0.00162544 step = 0.00017171 +In cycle 6: lambdaN = -0.00163487 step = 0.00000943 +In cycle 7: lambdaN = -0.00163490 step = 0.00000002 +In cycle 8: lambdaN = -0.00163490 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00163490 +Calculated stepsize too large ( 0.7559 > 0.1500). Scaled with 0.1984. +The final length of the internal step .... 0.1500 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0223606798 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0303142987 RMS(Int)= 0.0223058818 +done +Storing new coordinates .... done +The predicted energy change is .... 0.019364339 +Previously predicted energy change .... 0.005936457 +Actually observed energy change .... -0.000184379 +Ratio of predicted to observed change .... 0.031058800 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001843792 0.0000050000 NO + RMS gradient 0.0005225002 0.0001000000 NO + MAX gradient 0.0011302492 0.0003000000 NO + RMS step 0.0223606798 0.0020000000 NO + MAX step 0.0595334333 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0017 Max(Angles) 0.51 + Max(Dihed) 3.41 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5260 -0.000577 0.0005 1.5265 + 2. B(C 2,C 1) 1.5340 0.000805 -0.0012 1.5328 + 3. B(H 3,C 0) 1.3363 -0.000367 -0.0017 1.3347 0.56 + 4. B(H 3,C 1) 1.3174 0.000996 0.0001 1.3175 0.52 + 5. B(H 4,C 0) 1.0925 -0.000352 0.0001 1.0926 + 6. B(H 5,C 0) 1.0933 -0.000270 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0962 -0.000384 0.0002 1.0964 + 8. B(H 7,C 2) 1.1035 -0.000085 -0.0002 1.1033 + 9. B(H 8,C 2) 1.1009 -0.000160 0.0001 1.1010 + 10. B(H 9,C 2) 1.1048 -0.000146 0.0004 1.1051 + 11. A(C 1,C 0,H 3) 54.32 0.000609 0.02 54.33 0.30 + 12. A(C 1,C 0,H 5) 119.29 -0.000217 -0.00 119.29 + 13. A(H 3,C 0,H 4) 112.40 -0.000473 0.35 112.75 + 14. A(C 1,C 0,H 4) 117.79 -0.000329 0.10 117.89 + 15. A(H 4,C 0,H 5) 118.61 0.000399 -0.06 118.55 + 16. A(H 3,C 0,H 5) 117.85 0.000052 -0.39 117.46 + 17. A(C 0,C 1,H 3) 55.48 -0.000157 -0.09 55.39 0.31 + 18. A(H 3,C 1,H 6) 109.50 -0.000487 0.42 109.91 + 19. A(C 2,C 1,H 6) 117.76 -0.000464 0.14 117.90 + 20. A(C 0,C 1,H 6) 114.99 -0.000348 0.13 115.11 + 21. A(C 0,C 1,C 2) 121.74 0.000770 -0.22 121.53 + 22. A(C 2,C 1,H 3) 122.18 0.000901 -0.51 121.67 + 23. A(C 1,C 2,H 8) 110.26 -0.000053 0.06 110.32 + 24. A(C 1,C 2,H 7) 112.17 0.001044 -0.23 111.94 + 25. A(H 7,C 2,H 9) 107.45 -0.000144 0.02 107.46 + 26. A(C 1,C 2,H 9) 111.20 -0.000445 0.08 111.29 + 27. A(H 7,C 2,H 8) 107.69 -0.000405 0.09 107.78 + 28. A(H 8,C 2,H 9) 107.90 -0.000034 -0.02 107.87 + 29. A(C 0,H 3,C 1) 70.20 -0.000452 0.08 70.28 + 30. D(H 3,C 1,C 0,H 5) 104.87 0.000433 -0.50 104.37 + 31. D(C 2,C 1,C 0,H 4) 10.81 0.000843 -0.98 9.83 + 32. D(H 6,C 1,C 0,H 3) -97.26 0.000459 -0.41 -97.67 + 33. D(C 2,C 1,C 0,H 5) -145.59 0.001130 -1.08 -146.67 + 34. D(H 3,C 1,C 0,H 4) -98.74 0.000146 -0.39 -99.13 + 35. D(C 2,C 1,C 0,H 3) 109.55 0.000697 -0.58 108.96 + 36. D(H 7,C 2,C 1,C 0) -68.93 -0.000702 3.41 -65.52 + 37. D(H 8,C 2,C 1,H 6) 18.58 -0.000641 3.41 21.99 + 38. D(H 8,C 2,C 1,H 3) -122.39 -0.000357 3.41 -118.98 + 39. D(H 8,C 2,C 1,C 0) 171.06 -0.000844 3.41 174.47 + 40. D(H 7,C 2,C 1,H 6) 138.58 -0.000499 3.41 141.99 + 41. D(H 7,C 2,C 1,H 3) -2.38 -0.000215 3.41 1.03 + 42. D(C 0,H 3,C 1,C 2) -108.76 -0.000462 0.06 -108.70 + 43. D(C 1,H 3,C 0,H 5) -107.57 0.000107 -0.23 -107.80 + 44. D(C 1,H 3,C 0,H 4) 108.95 -0.000002 -0.08 108.87 + 45. D(C 0,H 3,C 1,H 6) 107.48 -0.000153 -0.11 107.37 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (13.536 %) +Internal coordinates : 0.000 s ( 2.008 %) +B/P matrices and projection : 0.000 s (14.929 %) +Hessian update/contruction : 0.000 s (13.731 %) +Making the step : 0.001 s (19.171 %) +Converting the step to Cartesian: 0.000 s ( 2.202 %) +Storing new data : 0.000 s ( 1.490 %) +Checking convergence : 0.000 s ( 0.680 %) +Final printing : 0.001 s (32.189 %) +Total time : 0.003 s + +Time for energy+gradient : 5.554 s +Time for complete geometry iter : 6.419 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 4 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.415564 -0.060665 0.023181 + C -0.020381 0.549795 -0.075367 + C 1.241363 -0.318994 -0.023366 + H -0.818439 0.674063 0.965092 + H -1.493721 -1.115746 0.296262 + H -2.240822 0.399262 -0.527085 + H 0.033970 1.500234 -0.619193 + H 1.363937 -0.809667 0.957210 + H 2.136493 0.295485 -0.205993 + H 1.213163 -1.113768 -0.790741 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.675028 -0.114640 0.043805 + 1 C 6.0000 0 12.011 -0.038514 1.038963 -0.142423 + 2 C 6.0000 0 12.011 2.345836 -0.602811 -0.044155 + 3 H 1.0000 0 1.008 -1.546625 1.273794 1.823760 + 4 H 1.0000 0 1.008 -2.822723 -2.108455 0.559854 + 5 H 1.0000 0 1.008 -4.234539 0.754496 -0.996047 + 6 H 1.0000 0 1.008 0.064193 2.835032 -1.170104 + 7 H 1.0000 0 1.008 2.577467 -1.530049 1.808864 + 8 H 1.0000 0 1.008 4.037388 0.558386 -0.389270 + 9 H 1.0000 0 1.008 2.292546 -2.104716 -1.494285 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526076456691 0.00000000 0.00000000 + C 2 1 0 1.532806349439 121.57642879 0.00000000 + H 2 1 3 1.317153701223 55.44494672 251.00116887 + H 1 2 3 1.092647509806 117.89159997 9.85513214 + H 1 2 3 1.093332474883 119.29419199 213.35308763 + H 2 1 3 1.096373196182 115.09535984 153.33402395 + H 3 2 1 1.103319060022 111.94209547 294.63448637 + H 3 2 1 1.100997731285 110.32105329 174.62264032 + H 3 2 1 1.105136206011 111.28810941 54.91478185 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.883866562571 0.00000000 0.00000000 + C 2 1 0 2.896584216776 121.57642879 0.00000000 + H 2 1 3 2.489059771593 55.44494672 251.00116887 + H 1 2 3 2.064804554444 117.89159997 9.85513214 + H 1 2 3 2.066098950852 119.29419199 213.35308763 + H 2 1 3 2.071845081357 115.09535984 153.33402395 + H 3 2 1 2.084970861778 111.94209547 294.63448637 + H 3 2 1 2.080584186198 110.32105329 174.62264032 + H 3 2 1 2.088404770041 111.28810941 54.91478185 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.763333475757 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.244e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40937 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5297 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10982 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24068 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2407 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.8631508615618344 0.00e+00 3.29e-04 2.49e-03 4.56e-03 0.700 0.1 + 2 -116.8632686234243039 -1.18e-04 3.26e-04 2.39e-03 3.61e-03 0.700 0.1 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -116.8633640837243917 -9.55e-05 9.49e-04 6.74e-03 2.71e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 4 -116.8636157541984772 -2.52e-04 1.29e-04 6.41e-04 4.49e-04 0.1 + 5 -116.8636181590811276 -2.40e-06 7.09e-05 4.12e-04 1.21e-04 0.1 + 6 -116.8636182260006109 -6.69e-08 2.77e-05 1.41e-04 1.25e-04 0.1 + 7 -116.8636183857916393 -1.60e-07 3.88e-06 3.38e-05 1.33e-05 0.1 + 8 -116.8636183877303978 -1.94e-09 2.70e-06 1.95e-05 4.53e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.112 sec) +Old exchange energy : -3.604460450 Eh +New exchange energy : -3.604471350 Eh +Exchange energy change after final integration : -0.000010900 Eh +Total energy after final integration : -116.863629287 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86362928724101 Eh -3180.02102 eV + +Components: +Nuclear Repulsion : 74.76333347575654 Eh 2034.41373 eV +Electronic Energy : -191.62695186348697 Eh -5214.43446 eV +One Electron Energy: -304.57085208766182 Eh -8287.79423 eV +Two Electron Energy: 112.94390022417487 Eh 3073.35977 eV + +Virial components: +Potential Energy : -232.18049000943682 Eh -6317.95233 eV +Kinetic Energy : 115.31686072219583 Eh 3137.93131 eV +Virial Ratio : 2.01341320389194 + +DFT components: +N(Alpha) : 13.000004326510 electrons +N(Beta) : 12.000004280652 electrons +N(Total) : 25.000008607163 electrons +E(X) : -14.252512601583 Eh +E(C) : -0.919755338156 Eh +E(XC) : -15.172267939739 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9388e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.9524e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.7034e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.7074e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.5321e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.1335e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762506 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012506 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.8 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.863629287241 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : -0.000028415 0.001242246 -0.001105061 + 2 C : 0.000075903 -0.001428989 0.000623085 + 3 C : -0.000019665 -0.000407290 -0.000227986 + 4 H : -0.001225835 0.000054008 0.000445202 + 5 H : 0.000356163 0.000391176 0.000560129 + 6 H : 0.000374561 -0.000370831 -0.000465492 + 7 H : -0.000074209 0.000177688 0.000832507 + 8 H : 0.000815514 0.000502515 0.000075485 + 9 H : -0.000173246 -0.000213039 -0.000764849 + 10 H : -0.000100770 0.000052517 0.000026981 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000388711 0.0000388972 0.0000046860 + +Norm of the Cartesian gradient ... 0.0032463466 +RMS gradient ... 0.0005926991 +MAX gradient ... 0.0014289893 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.666 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.118 sec ( 17.7%) +COSX gradient .... 0.418 sec ( 62.7%) +XC gradient .... 0.125 sec ( 18.8%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.863629287 Eh +Current gradient norm .... 0.003246347 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124716293 0.000427036 0.027985192 0.042188356 0.052641920 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12471629 and components: + 1. 0.00330039 + 2. 0.04861719 + 3. 0.55527745 + 4. -0.51888030 + 5. -0.01022174 + 6. -0.01338895 + 7. -0.00012007 + 8. -0.00674627 + 9. 0.00155737 + 10. -0.00817403 + 11. -0.29872391 + 12. 0.01842088 + 13. 0.00384348 + 14. -0.00959517 + 15. 0.07011366 + 16. 0.01708032 + 17. 0.31181879 + 18. 0.03268714 + 19. -0.04636678 + 20. 0.03143197 + 21. -0.06041967 + 22. -0.09289871 + 23. 0.00535700 + 24. -0.02167589 + 25. 0.00854949 + 26. 0.01347055 + 27. 0.00219339 + 28. -0.00776726 + 29. -0.01309488 + 30. -0.10063435 + 31. 0.15570848 + 32. -0.14353783 + 33. -0.06176246 + 34. 0.11683659 + 35. 0.03887189 + 36. -0.16346453 + 37. 0.01184022 + 38. 0.17225103 + 39. -0.15549647 + 40. 0.00387216 + 41. 0.16428296 + 42. -0.10857194 + 43. 0.09027588 + 44. -0.06777426 + 45. 0.06214900 + +Lambda that maximizes along the TS mode: 0.00000464 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00040335 step = 0.00040335 +In cycle 2: lambdaN = -0.00099202 step = 0.00058867 +In cycle 3: lambdaN = -0.00139843 step = 0.00040641 +In cycle 4: lambdaN = -0.00146501 step = 0.00006658 +In cycle 5: lambdaN = -0.00146609 step = 0.00000107 +In cycle 6: lambdaN = -0.00146609 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00146609 +Calculated stepsize too large ( 0.7548 > 0.1000). Scaled with 0.1325. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0201192153 RMS(Int)= 0.0148826659 +done +Storing new coordinates .... done +The predicted energy change is .... 0.006625931 +Previously predicted energy change .... 0.019364339 +Actually observed energy change .... -0.000266394 +Ratio of predicted to observed change .... 0.013756938 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0002663940 0.0000050000 NO + RMS gradient 0.0004434797 0.0001000000 NO + MAX gradient 0.0009240836 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0397431679 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.34 + Max(Dihed) 2.28 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5261 -0.000645 0.0003 1.5264 + 2. B(C 2,C 1) 1.5328 0.000437 -0.0006 1.5322 + 3. B(H 3,C 0) 1.3355 -0.000367 -0.0006 1.3349 0.56 + 4. B(H 3,C 1) 1.3172 0.000813 0.0000 1.3172 0.52 + 5. B(H 4,C 0) 1.0926 -0.000264 0.0000 1.0927 + 6. B(H 5,C 0) 1.0933 -0.000204 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0964 -0.000262 0.0000 1.0964 + 8. B(H 7,C 2) 1.1033 -0.000064 -0.0001 1.1032 + 9. B(H 8,C 2) 1.1010 -0.000133 0.0001 1.1011 + 10. B(H 9,C 2) 1.1051 -0.000055 0.0002 1.1053 + 11. A(C 1,C 0,H 3) 54.32 0.000549 0.00 54.32 0.30 + 12. A(C 1,C 0,H 5) 119.29 -0.000094 -0.04 119.25 + 13. A(H 3,C 0,H 4) 112.76 -0.000388 0.25 113.02 + 14. A(C 1,C 0,H 4) 117.89 -0.000295 0.09 117.99 + 15. A(H 4,C 0,H 5) 118.55 0.000270 -0.03 118.52 + 16. A(H 3,C 0,H 5) 117.45 0.000047 -0.26 117.19 + 17. A(C 0,C 1,H 3) 55.44 -0.000114 -0.04 55.41 0.31 + 18. A(H 3,C 1,H 6) 109.88 -0.000439 0.28 110.16 + 19. A(C 2,C 1,H 6) 117.86 -0.000380 0.08 117.94 + 20. A(C 0,C 1,H 6) 115.10 -0.000358 0.10 115.20 + 21. A(C 0,C 1,C 2) 121.58 0.000697 -0.15 121.43 + 22. A(C 2,C 1,H 3) 121.70 0.000777 -0.34 121.35 + 23. A(C 1,C 2,H 8) 110.32 -0.000144 0.06 110.39 + 24. A(C 1,C 2,H 7) 111.94 0.000743 -0.15 111.80 + 25. A(H 7,C 2,H 9) 107.47 -0.000096 0.01 107.47 + 26. A(C 1,C 2,H 9) 111.29 -0.000262 0.04 111.33 + 27. A(H 7,C 2,H 8) 107.78 -0.000250 0.06 107.84 + 28. A(H 8,C 2,H 9) 107.87 -0.000013 -0.02 107.85 + 29. A(C 0,H 3,C 1) 70.24 -0.000435 0.03 70.27 + 30. D(H 3,C 1,C 0,H 5) 104.35 0.000335 -0.31 104.04 + 31. D(C 2,C 1,C 0,H 4) 9.86 0.000675 -0.65 9.21 + 32. D(H 6,C 1,C 0,H 3) -97.67 0.000375 -0.27 -97.94 + 33. D(C 2,C 1,C 0,H 5) -146.65 0.000924 -0.69 -147.34 + 34. D(H 3,C 1,C 0,H 4) -99.14 0.000085 -0.27 -99.41 + 35. D(C 2,C 1,C 0,H 3) 109.00 0.000589 -0.38 108.62 + 36. D(H 7,C 2,C 1,C 0) -65.37 -0.000726 2.28 -63.09 + 37. D(H 8,C 2,C 1,H 6) 21.99 -0.000598 2.28 24.27 + 38. D(H 8,C 2,C 1,H 3) -119.14 -0.000350 2.28 -116.86 + 39. D(H 8,C 2,C 1,C 0) 174.62 -0.000802 2.28 176.90 + 40. D(H 7,C 2,C 1,H 6) 142.00 -0.000522 2.28 144.28 + 41. D(H 7,C 2,C 1,H 3) 0.87 -0.000274 2.28 3.15 + 42. D(C 0,H 3,C 1,C 2) -108.78 -0.000446 0.03 -108.75 + 43. D(C 1,H 3,C 0,H 5) -107.80 -0.000025 -0.10 -107.90 + 44. D(C 1,H 3,C 0,H 4) 108.86 -0.000020 -0.04 108.82 + 45. D(C 0,H 3,C 1,H 6) 107.37 -0.000190 -0.05 107.32 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.000 s (16.696 %) +Internal coordinates : 0.000 s ( 2.113 %) +B/P matrices and projection : 0.000 s (13.301 %) +Hessian update/contruction : 0.000 s (13.717 %) +Making the step : 0.001 s (19.259 %) +Converting the step to Cartesian: 0.000 s ( 2.148 %) +Storing new data : 0.000 s ( 1.489 %) +Checking convergence : 0.000 s ( 0.658 %) +Final printing : 0.001 s (30.481 %) +Total time : 0.003 s + +Time for energy+gradient : 5.726 s +Time for complete geometry iter : 6.590 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 5 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.414328 -0.061080 0.029731 + C -0.020416 0.549789 -0.083804 + C 1.240471 -0.318671 -0.024451 + H -0.811361 0.682413 0.960810 + H -1.491215 -1.114931 0.308063 + H -2.244312 0.396893 -0.514968 + H 0.031726 1.493129 -0.640140 + H 1.342181 -0.827036 0.949336 + H 2.139050 0.298890 -0.177796 + H 1.228204 -1.099396 -0.806781 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.672693 -0.115424 0.056184 + 1 C 6.0000 0 12.011 -0.038580 1.038950 -0.158366 + 2 C 6.0000 0 12.011 2.344150 -0.602201 -0.046206 + 3 H 1.0000 0 1.008 -1.533251 1.289574 1.815668 + 4 H 1.0000 0 1.008 -2.817987 -2.106915 0.582155 + 5 H 1.0000 0 1.008 -4.241135 0.750019 -0.973148 + 6 H 1.0000 0 1.008 0.059953 2.821605 -1.209690 + 7 H 1.0000 0 1.008 2.536355 -1.562872 1.793985 + 8 H 1.0000 0 1.008 4.042218 0.564819 -0.335985 + 9 H 1.0000 0 1.008 2.320970 -2.077556 -1.524596 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526119927973 0.00000000 0.00000000 + C 2 1 0 1.532181186756 121.45855459 0.00000000 + H 2 1 3 1.316966943387 55.44111390 251.35808981 + H 1 2 3 1.092695303817 117.98656871 9.22296117 + H 1 2 3 1.093302145941 119.25202172 212.67704878 + H 2 1 3 1.096412406003 115.18726975 153.41487133 + H 3 2 1 1.103196383186 111.79324147 297.00639419 + H 3 2 1 1.101062989730 110.38288626 176.98661686 + H 3 2 1 1.105315179759 111.33437406 57.22966636 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.883948711389 0.00000000 0.00000000 + C 2 1 0 2.895402830515 121.45855459 0.00000000 + H 2 1 3 2.488706850429 55.44111390 251.35808981 + H 1 2 3 2.064894872036 117.98656871 9.22296117 + H 1 2 3 2.066041637457 119.25202172 212.67704878 + H 2 1 3 2.071919177179 115.18726975 153.41487133 + H 3 2 1 2.084739036154 111.79324147 297.00639419 + H 3 2 1 2.080707506787 110.38288626 176.98661686 + H 3 2 1 2.088742981411 111.33437406 57.22966636 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.780019697471 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.244e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40933 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4093 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5298 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10974 +Total number of batches ... 90 +Average number of points per batch ... 121 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24061 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8635762591212028 0.00e+00 7.27e-04 5.53e-03 7.66e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8637565595339822 -1.80e-04 3.68e-04 2.30e-03 1.00e-03 0.1 + 3 -116.8637811388803414 -2.46e-05 7.29e-05 3.96e-04 1.82e-04 0.1 + 4 -116.8637817512301069 -6.12e-07 1.49e-05 9.29e-05 2.97e-05 0.1 + 5 -116.8637817625495643 -1.13e-08 6.34e-06 4.65e-05 3.19e-05 0.1 + 6 -116.8637817697239711 -7.17e-09 1.77e-06 1.48e-05 6.48e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 6 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.099 sec) +Old exchange energy : -3.604489206 Eh +New exchange energy : -3.604504990 Eh +Exchange energy change after final integration : -0.000015785 Eh +Total energy after final integration : -116.863797554 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86379755434756 Eh -3180.02560 eV + +Components: +Nuclear Repulsion : 74.78001969747100 Eh 2034.86779 eV +Electronic Energy : -191.64380146719498 Eh -5214.89296 eV +One Electron Energy: -304.60349769094398 Eh -8288.68256 eV +Two Electron Energy: 112.95969622374901 Eh 3073.78960 eV + +Virial components: +Potential Energy : -232.18069612221848 Eh -6317.95794 eV +Kinetic Energy : 115.31689856787092 Eh 3137.93234 eV +Virial Ratio : 2.01341433047270 + +DFT components: +N(Alpha) : 13.000004950719 electrons +N(Beta) : 12.000004843400 electrons +N(Total) : 25.000009794120 electrons +E(X) : -14.252601501271 Eh +E(C) : -0.919771103700 Eh +E(XC) : -15.172372604971 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 7.1744e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.4815e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.7743e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.0168e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 6.4777e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.3495e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762491 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012491 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 1.0 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 6.9 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.863797554348 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000264896 0.001258185 -0.000936515 + 2 C : 0.000189227 -0.001349766 0.000493310 + 3 C : -0.000157913 -0.000454135 -0.000242591 + 4 H : -0.001318437 -0.000006872 0.000438121 + 5 H : 0.000279251 0.000327483 0.000441959 + 6 H : 0.000303155 -0.000343998 -0.000374598 + 7 H : -0.000060566 0.000176663 0.000783192 + 8 H : 0.000720752 0.000544583 0.000136397 + 9 H : -0.000168811 -0.000177017 -0.000758872 + 10 H : -0.000051554 0.000024874 0.000019596 + +Difference to translation invariance: + : -0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000437441 0.0000098085 -0.0000088846 + +Norm of the Cartesian gradient ... 0.0031152868 +RMS gradient ... 0.0005687709 +MAX gradient ... 0.0013497664 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.681 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.7%) +RI-J Coulomb gradient .... 0.117 sec ( 17.1%) +COSX gradient .... 0.420 sec ( 61.6%) +XC gradient .... 0.139 sec ( 20.5%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.863797554 Eh +Current gradient norm .... 0.003115287 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124723948 0.000677996 0.027969097 0.042185042 0.052637079 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12472395 and components: + 1. 0.00330887 + 2. 0.04857339 + 3. 0.55525175 + 4. -0.51887650 + 5. -0.01022058 + 6. -0.01339105 + 7. -0.00011676 + 8. -0.00675718 + 9. 0.00156439 + 10. -0.00815963 + 11. -0.29872064 + 12. 0.01837149 + 13. 0.00406279 + 14. -0.00951309 + 15. 0.07008872 + 16. 0.01686390 + 17. 0.31180513 + 18. 0.03290061 + 19. -0.04632715 + 20. 0.03150771 + 21. -0.06051003 + 22. -0.09315665 + 23. 0.00541690 + 24. -0.02178068 + 25. 0.00855403 + 26. 0.01349067 + 27. 0.00222965 + 28. -0.00778153 + 29. -0.01308449 + 30. -0.10088385 + 31. 0.15518514 + 32. -0.14375627 + 33. -0.06230099 + 34. 0.11660228 + 35. 0.03858286 + 36. -0.16144413 + 37. 0.01376319 + 38. 0.17409958 + 39. -0.15349325 + 40. 0.00581230 + 41. 0.16614869 + 42. -0.10858493 + 43. 0.09020934 + 44. -0.06780590 + 45. 0.06211070 + +Lambda that maximizes along the TS mode: 0.00000618 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00057810 step = 0.00057810 +In cycle 2: lambdaN = -0.00113517 step = 0.00055707 +In cycle 3: lambdaN = -0.00128809 step = 0.00015292 +In cycle 4: lambdaN = -0.00129354 step = 0.00000545 +In cycle 5: lambdaN = -0.00129355 step = 0.00000001 +Lambda that minimizes along all other modes: -0.00129355 +Calculated stepsize too large ( 0.7528 > 0.1000). Scaled with 0.1328. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0200783792 RMS(Int)= 0.0148845305 +done +Storing new coordinates .... done +The predicted energy change is .... 0.006210785 +Previously predicted energy change .... 0.006625931 +Actually observed energy change .... -0.000168267 +Ratio of predicted to observed change .... 0.025395239 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001682671 0.0000050000 NO + RMS gradient 0.0004120009 0.0001000000 NO + MAX gradient 0.0008408236 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0398528471 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0007 Max(Angles) 0.32 + Max(Dihed) 2.28 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5261 -0.000703 0.0003 1.5264 + 2. B(C 2,C 1) 1.5322 0.000284 -0.0005 1.5316 + 3. B(H 3,C 0) 1.3354 -0.000430 -0.0007 1.3347 0.56 + 4. B(H 3,C 1) 1.3170 0.000841 0.0002 1.3172 0.52 + 5. B(H 4,C 0) 1.0927 -0.000223 0.0000 1.0927 + 6. B(H 5,C 0) 1.0933 -0.000188 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0964 -0.000248 0.0001 1.0965 + 8. B(H 7,C 2) 1.1032 -0.000063 -0.0001 1.1031 + 9. B(H 8,C 2) 1.1011 -0.000131 0.0001 1.1012 + 10. B(H 9,C 2) 1.1053 -0.000032 0.0002 1.1055 + 11. A(C 1,C 0,H 3) 54.31 0.000583 0.01 54.32 0.30 + 12. A(C 1,C 0,H 5) 119.25 -0.000074 -0.06 119.19 + 13. A(H 3,C 0,H 4) 113.03 -0.000333 0.26 113.28 + 14. A(C 1,C 0,H 4) 117.99 -0.000246 0.10 118.09 + 15. A(H 4,C 0,H 5) 118.52 0.000204 -0.04 118.49 + 16. A(H 3,C 0,H 5) 117.19 0.000010 -0.24 116.95 + 17. A(C 0,C 1,H 3) 55.44 -0.000130 -0.04 55.40 0.31 + 18. A(H 3,C 1,H 6) 110.14 -0.000390 0.26 110.40 + 19. A(C 2,C 1,H 6) 117.92 -0.000345 0.07 117.98 + 20. A(C 0,C 1,H 6) 115.19 -0.000331 0.10 115.29 + 21. A(C 0,C 1,C 2) 121.46 0.000643 -0.13 121.33 + 22. A(C 2,C 1,H 3) 121.37 0.000711 -0.32 121.05 + 23. A(C 1,C 2,H 8) 110.38 -0.000157 0.07 110.46 + 24. A(C 1,C 2,H 7) 111.79 0.000564 -0.13 111.66 + 25. A(H 7,C 2,H 9) 107.48 -0.000076 0.00 107.48 + 26. A(C 1,C 2,H 9) 111.33 -0.000147 0.02 111.36 + 27. A(H 7,C 2,H 8) 107.83 -0.000183 0.05 107.88 + 28. A(H 8,C 2,H 9) 107.86 -0.000018 -0.02 107.84 + 29. A(C 0,H 3,C 1) 70.25 -0.000453 0.03 70.28 + 30. D(H 3,C 1,C 0,H 5) 104.04 0.000290 -0.27 103.76 + 31. D(C 2,C 1,C 0,H 4) 9.22 0.000554 -0.64 8.58 + 32. D(H 6,C 1,C 0,H 3) -97.94 0.000337 -0.25 -98.19 + 33. D(C 2,C 1,C 0,H 5) -147.32 0.000813 -0.63 -147.96 + 34. D(H 3,C 1,C 0,H 4) -99.42 0.000031 -0.28 -99.70 + 35. D(C 2,C 1,C 0,H 3) 108.64 0.000523 -0.36 108.28 + 36. D(H 7,C 2,C 1,C 0) -62.99 -0.000704 2.28 -60.71 + 37. D(H 8,C 2,C 1,H 6) 24.26 -0.000562 2.28 26.55 + 38. D(H 8,C 2,C 1,H 3) -116.96 -0.000363 2.28 -114.67 + 39. D(H 8,C 2,C 1,C 0) 176.99 -0.000740 2.28 179.27 + 40. D(H 7,C 2,C 1,H 6) 144.28 -0.000527 2.28 146.57 + 41. D(H 7,C 2,C 1,H 3) 3.06 -0.000328 2.28 5.35 + 42. D(C 0,H 3,C 1,C 2) -108.80 -0.000401 0.02 -108.78 + 43. D(C 1,H 3,C 0,H 5) -107.90 -0.000079 -0.07 -107.97 + 44. D(C 1,H 3,C 0,H 4) 108.82 0.000016 -0.03 108.78 + 45. D(C 0,H 3,C 1,H 6) 107.32 -0.000191 -0.04 107.29 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s ( 5.199 %) +Internal coordinates : 0.000 s ( 0.403 %) +B/P matrices and projection : 0.000 s ( 3.783 %) +Hessian update/contruction : 0.000 s ( 3.801 %) +Making the step : 0.001 s ( 5.011 %) +Converting the step to Cartesian: 0.000 s ( 0.636 %) +Storing new data : 0.000 s ( 0.412 %) +Checking convergence : 0.000 s ( 0.170 %) +Final printing : 0.009 s (80.556 %) +Total time : 0.011 s + +Time for energy+gradient : 5.491 s +Time for complete geometry iter : 6.336 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 6 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.413169 -0.061360 0.036520 + C -0.020555 0.549551 -0.092123 + C 1.239696 -0.318345 -0.025547 + H -0.804651 0.690917 0.956515 + H -1.489045 -1.113892 0.320243 + H -2.247369 0.394588 -0.503413 + H 0.029339 1.485667 -0.660862 + H 1.321124 -0.844485 0.940552 + H 2.141047 0.301932 -0.149485 + H 1.243584 -1.084572 -0.822399 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.670502 -0.115954 0.069012 + 1 C 6.0000 0 12.011 -0.038843 1.038501 -0.174088 + 2 C 6.0000 0 12.011 2.342686 -0.601586 -0.048278 + 3 H 1.0000 0 1.008 -1.520571 1.305643 1.807551 + 4 H 1.0000 0 1.008 -2.813888 -2.104952 0.605171 + 5 H 1.0000 0 1.008 -4.246913 0.745664 -0.951312 + 6 H 1.0000 0 1.008 0.055443 2.807504 -1.248848 + 7 H 1.0000 0 1.008 2.496562 -1.595846 1.777386 + 8 H 1.0000 0 1.008 4.045992 0.570569 -0.282485 + 9 H 1.0000 0 1.008 2.350033 -2.049545 -1.554109 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526149931543 0.00000000 0.00000000 + C 2 1 0 1.531636402360 121.35427284 0.00000000 + H 2 1 3 1.316978671108 55.42880300 251.69525581 + H 1 2 3 1.092739823705 118.08715982 8.59951727 + H 1 2 3 1.093301046551 119.18831387 212.05867011 + H 2 1 3 1.096479335542 115.27706042 153.49763715 + H 3 2 1 1.103087588609 111.65894187 299.38513113 + H 3 2 1 1.101152853521 110.45258999 179.35537358 + H 3 2 1 1.105482444225 111.36531336 59.54930389 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.884005409919 0.00000000 0.00000000 + C 2 1 0 2.894373337204 121.35427284 0.00000000 + H 2 1 3 2.488729012609 55.42880300 251.69525581 + H 1 2 3 2.064979002432 118.08715982 8.59951727 + H 1 2 3 2.066039559911 119.18831387 212.05867011 + H 2 1 3 2.072045655678 115.27706042 153.49763715 + H 3 2 1 2.084533444199 111.65894187 299.38513113 + H 3 2 1 2.080877324741 110.45258999 179.35537358 + H 3 2 1 2.089059065443 111.36531336 59.54930389 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.794483870559 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.243e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40942 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5299 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10973 +Total number of batches ... 90 +Average number of points per batch ... 121 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24058 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8637297207087471 0.00e+00 7.24e-04 5.54e-03 7.67e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8639095383883983 -1.80e-04 3.67e-04 2.30e-03 1.00e-03 0.1 + 3 -116.8639340716756152 -2.45e-05 7.35e-05 3.91e-04 2.00e-04 0.1 + 4 -116.8639346948849180 -6.23e-07 1.88e-05 1.19e-04 4.26e-05 0.1 + 5 -116.8639347061702978 -1.13e-08 7.45e-06 5.02e-05 4.03e-05 0.1 + 6 -116.8639347188125015 -1.26e-08 1.56e-06 1.37e-05 4.91e-06 0.1 + 7 -116.8639347194547753 -6.42e-10 9.83e-07 8.46e-06 1.74e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.604505656 Eh +New exchange energy : -3.604525649 Eh +Exchange energy change after final integration : -0.000019992 Eh +Total energy after final integration : -116.863954712 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86395471163110 Eh -3180.02988 eV + +Components: +Nuclear Repulsion : 74.79448387055943 Eh 2035.26138 eV +Electronic Energy : -191.65841859001421 Eh -5215.29071 eV +One Electron Energy: -304.63176400995758 Eh -8289.45173 eV +Two Electron Energy: 112.97334541994337 Eh 3074.16102 eV + +Virial components: +Potential Energy : -232.18081448671953 Eh -6317.96116 eV +Kinetic Energy : 115.31685977508843 Eh 3137.93128 eV +Virial Ratio : 2.01341603421703 + +DFT components: +N(Alpha) : 13.000004288555 electrons +N(Beta) : 12.000004065566 electrons +N(Total) : 25.000008354121 electrons +E(X) : -14.252650223993 Eh +E(C) : -0.919783257097 Eh +E(XC) : -15.172433481090 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.4227e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 8.4571e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 9.8347e-07 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9873e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.7351e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 7.8547e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762479 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012479 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.0 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.863954711631 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000522452 0.001181822 -0.000792321 + 2 C : 0.000176970 -0.001259425 0.000412166 + 3 C : -0.000268301 -0.000490802 -0.000262287 + 4 H : -0.001306758 -0.000007745 0.000435787 + 5 H : 0.000189715 0.000269390 0.000324047 + 6 H : 0.000244053 -0.000304291 -0.000312402 + 7 H : -0.000044588 0.000188792 0.000719585 + 8 H : 0.000652641 0.000564084 0.000195611 + 9 H : -0.000148292 -0.000144275 -0.000727163 + 10 H : -0.000017890 0.000002449 0.000006977 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000437206 -0.0000160680 -0.0000165816 + +Norm of the Cartesian gradient ... 0.0029558635 +RMS gradient ... 0.0005396644 +MAX gradient ... 0.0013067583 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.650 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.7%) +RI-J Coulomb gradient .... 0.113 sec ( 17.4%) +COSX gradient .... 0.412 sec ( 63.4%) +XC gradient .... 0.120 sec ( 18.4%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.863954712 Eh +Current gradient norm .... 0.002955864 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124722846 0.000818712 0.027973761 0.042196635 0.052636063 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12472285 and components: + 1. -0.00330452 + 2. -0.04859556 + 3. -0.55526557 + 4. 0.51888044 + 5. 0.01022102 + 6. 0.01338960 + 7. 0.00011811 + 8. 0.00675179 + 9. -0.00156129 + 10. 0.00816691 + 11. 0.29872323 + 12. -0.01839789 + 13. -0.00395406 + 14. 0.00955210 + 15. -0.07010141 + 16. -0.01696588 + 17. -0.31181270 + 18. -0.03279673 + 19. 0.04634753 + 20. -0.03146983 + 21. 0.06046460 + 22. 0.09303035 + 23. -0.00538850 + 24. 0.02172864 + 25. -0.00855182 + 26. -0.01347943 + 27. -0.00221117 + 28. 0.00777413 + 29. 0.01308947 + 30. 0.10076842 + 31. -0.15544421 + 32. 0.14365100 + 33. 0.06204407 + 34. -0.11671986 + 35. -0.03872435 + 36. 0.16247927 + 37. -0.01277735 + 38. -0.17315071 + 39. 0.15452002 + 40. -0.00481810 + 41. -0.16519146 + 42. 0.10858089 + 43. -0.09023676 + 44. 0.06778805 + 45. -0.06212850 + +Lambda that maximizes along the TS mode: 0.00000621 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00063403 step = 0.00063403 +In cycle 2: lambdaN = -0.00107728 step = 0.00044325 +In cycle 3: lambdaN = -0.00114402 step = 0.00006674 +In cycle 4: lambdaN = -0.00114490 step = 0.00000088 +In cycle 5: lambdaN = -0.00114490 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00114490 +Calculated stepsize too large ( 0.7398 > 0.1000). Scaled with 0.1352. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0201397888 RMS(Int)= 0.9305879859 +done +Storing new coordinates .... done +The predicted energy change is .... 0.001803016 +Previously predicted energy change .... 0.006210785 +Actually observed energy change .... -0.000157157 +Ratio of predicted to observed change .... 0.025303932 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001571573 0.0000050000 NO + RMS gradient 0.0003817180 0.0001000000 NO + MAX gradient 0.0008149920 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0405525964 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.29 + Max(Dihed) 2.32 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5261 -0.000754 0.0003 1.5264 + 2. B(C 2,C 1) 1.5316 0.000184 -0.0005 1.5312 + 3. B(H 3,C 0) 1.3351 -0.000430 -0.0006 1.3345 0.56 + 4. B(H 3,C 1) 1.3170 0.000815 0.0002 1.3172 0.52 + 5. B(H 4,C 0) 1.0927 -0.000188 0.0000 1.0928 + 6. B(H 5,C 0) 1.0933 -0.000160 0.0000 1.0933 + 7. B(H 6,C 1) 1.0965 -0.000214 0.0001 1.0965 + 8. B(H 7,C 2) 1.1031 -0.000050 -0.0001 1.1030 + 9. B(H 8,C 2) 1.1012 -0.000121 0.0001 1.1012 + 10. B(H 9,C 2) 1.1055 -0.000007 0.0001 1.1056 + 11. A(C 1,C 0,H 3) 54.31 0.000585 0.01 54.32 0.30 + 12. A(C 1,C 0,H 5) 119.19 -0.000072 -0.07 119.12 + 13. A(H 3,C 0,H 4) 113.29 -0.000260 0.25 113.54 + 14. A(C 1,C 0,H 4) 118.09 -0.000183 0.10 118.18 + 15. A(H 4,C 0,H 5) 118.49 0.000140 -0.03 118.45 + 16. A(H 3,C 0,H 5) 116.94 -0.000023 -0.23 116.72 + 17. A(C 0,C 1,H 3) 55.43 -0.000113 -0.04 55.39 0.31 + 18. A(H 3,C 1,H 6) 110.39 -0.000347 0.24 110.63 + 19. A(C 2,C 1,H 6) 117.96 -0.000308 0.05 118.01 + 20. A(C 0,C 1,H 6) 115.28 -0.000302 0.10 115.37 + 21. A(C 0,C 1,C 2) 121.35 0.000577 -0.11 121.24 + 22. A(C 2,C 1,H 3) 121.07 0.000636 -0.29 120.78 + 23. A(C 1,C 2,H 8) 110.45 -0.000158 0.08 110.53 + 24. A(C 1,C 2,H 7) 111.66 0.000439 -0.12 111.54 + 25. A(H 7,C 2,H 9) 107.48 -0.000056 0.00 107.49 + 26. A(C 1,C 2,H 9) 111.37 -0.000069 0.01 111.38 + 27. A(H 7,C 2,H 8) 107.87 -0.000148 0.05 107.92 + 28. A(H 8,C 2,H 9) 107.84 -0.000022 -0.02 107.83 + 29. A(C 0,H 3,C 1) 70.26 -0.000471 0.03 70.29 + 30. D(H 3,C 1,C 0,H 5) 103.75 0.000247 -0.24 103.51 + 31. D(C 2,C 1,C 0,H 4) 8.60 0.000444 -0.59 8.01 + 32. D(H 6,C 1,C 0,H 3) -98.20 0.000294 -0.23 -98.43 + 33. D(C 2,C 1,C 0,H 5) -147.94 0.000714 -0.57 -148.52 + 34. D(H 3,C 1,C 0,H 4) -99.71 -0.000023 -0.26 -99.97 + 35. D(C 2,C 1,C 0,H 3) 108.30 0.000467 -0.33 107.97 + 36. D(H 7,C 2,C 1,C 0) -60.61 -0.000690 2.32 -58.29 + 37. D(H 8,C 2,C 1,H 6) 26.54 -0.000520 2.31 28.85 + 38. D(H 8,C 2,C 1,H 3) -114.76 -0.000350 2.22 -112.55 + 39. D(H 8,C 2,C 1,C 0) 179.36 -0.000687 2.32 181.68 + 40. D(H 7,C 2,C 1,H 6) 146.57 -0.000523 2.32 148.89 + 41. D(H 7,C 2,C 1,H 3) 5.27 -0.000353 2.25 7.52 + 42. D(C 0,H 3,C 1,C 2) -108.82 -0.000360 0.01 -108.81 + 43. D(C 1,H 3,C 0,H 5) -107.97 -0.000098 -0.05 -108.01 + 44. D(C 1,H 3,C 0,H 4) 108.78 0.000054 -0.03 108.75 + 45. D(C 0,H 3,C 1,H 6) 107.28 -0.000180 -0.03 107.25 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (19.453 %) +Internal coordinates : 0.000 s ( 1.413 %) +B/P matrices and projection : 0.000 s (13.139 %) +Hessian update/contruction : 0.000 s (12.447 %) +Making the step : 0.001 s (17.078 %) +Converting the step to Cartesian: 0.000 s ( 2.375 %) +Storing new data : 0.000 s ( 1.503 %) +Checking convergence : 0.000 s ( 0.571 %) +Final printing : 0.001 s (31.930 %) +Total time : 0.003 s + +Time for energy+gradient : 5.596 s +Time for complete geometry iter : 6.437 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 7 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.412053 -0.061515 0.043418 + C -0.020690 0.549261 -0.100258 + C 1.239010 -0.318015 -0.026624 + H -0.798313 0.699550 0.952074 + H -1.486968 -1.112553 0.333034 + H -2.250126 0.392178 -0.492406 + H 0.026858 1.477922 -0.681394 + H 1.300566 -0.862176 0.930793 + H 2.142497 0.304524 -0.120999 + H 1.259219 -1.069176 -0.837639 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.668393 -0.116247 0.082049 + 1 C 6.0000 0 12.011 -0.039099 1.037953 -0.189460 + 2 C 6.0000 0 12.011 2.341390 -0.600962 -0.050311 + 3 H 1.0000 0 1.008 -1.508593 1.321958 1.799160 + 4 H 1.0000 0 1.008 -2.809961 -2.102420 0.629343 + 5 H 1.0000 0 1.008 -4.252122 0.741109 -0.930512 + 6 H 1.0000 0 1.008 0.050754 2.792867 -1.287649 + 7 H 1.0000 0 1.008 2.457713 -1.629277 1.758943 + 8 H 1.0000 0 1.008 4.048733 0.575468 -0.228655 + 9 H 1.0000 0 1.008 2.379579 -2.020449 -1.582907 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526295824533 0.00000000 0.00000000 + C 2 1 0 1.531154806240 121.25108519 0.00000000 + H 2 1 3 1.317075350398 55.40516590 252.00600966 + H 1 2 3 1.092780481017 118.18530259 8.01836186 + H 1 2 3 1.093303383025 119.11662677 211.49660634 + H 2 1 3 1.096535917661 115.36112292 153.56274429 + H 3 2 1 1.102971313078 111.53734738 301.77232782 + H 3 2 1 1.101249911856 110.52706939 181.72168589 + H 3 2 1 1.105620163157 111.38222177 61.87114610 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.884281107716 0.00000000 0.00000000 + C 2 1 0 2.893463252430 121.25108519 0.00000000 + H 2 1 3 2.488911709990 55.40516590 252.00600966 + H 1 2 3 2.065055833617 118.18530259 8.01836186 + H 1 2 3 2.066043975207 119.11662677 211.49660634 + H 2 1 3 2.072152580388 115.36112292 153.56274429 + H 3 2 1 2.084313715290 111.53734738 301.77232782 + H 3 2 1 2.081060738413 110.52706939 181.72168589 + H 3 2 1 2.089319316509 111.38222177 61.87114610 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.806756928100 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.243e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40945 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5296 +Total number of batches ... 49 +Average number of points per batch ... 108 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10970 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24056 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8638712042229457 0.00e+00 7.26e-04 5.56e-03 7.82e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8640520706657497 -1.81e-04 3.67e-04 2.31e-03 1.02e-03 0.1 + 3 -116.8640767349395588 -2.47e-05 7.42e-05 3.87e-04 2.10e-04 0.1 + 4 -116.8640773686509391 -6.34e-07 2.12e-05 1.34e-04 5.03e-05 0.1 + 5 -116.8640773803337964 -1.17e-08 8.25e-06 5.23e-05 4.44e-05 0.1 + 6 -116.8640773966565831 -1.63e-08 1.70e-06 1.41e-05 4.66e-06 0.1 + 7 -116.8640773970313802 -3.75e-10 1.15e-06 9.63e-06 1.90e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.095 sec) +Old exchange energy : -3.604513536 Eh +New exchange energy : -3.604536894 Eh +Exchange energy change after final integration : -0.000023358 Eh +Total energy after final integration : -116.864100755 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86410075535942 Eh -3180.03385 eV + +Components: +Nuclear Repulsion : 74.80675692809983 Eh 2035.59534 eV +Electronic Energy : -191.67083432513121 Eh -5215.62856 eV +One Electron Energy: -304.65572219872018 Eh -8290.10366 eV +Two Electron Energy: 112.98488787358897 Eh 3074.47510 eV + +Virial components: +Potential Energy : -232.18082296602444 Eh -6317.96139 eV +Kinetic Energy : 115.31672221066503 Eh 3137.92754 eV +Virial Ratio : 2.01341850960581 + +DFT components: +N(Alpha) : 13.000002535543 electrons +N(Beta) : 12.000002162182 electrons +N(Total) : 25.000004697725 electrons +E(X) : -14.252669979482 Eh +E(C) : -0.919793189022 Eh +E(XC) : -15.172463168504 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 3.7480e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.6307e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1452e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9657e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.8951e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 8.9732e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762466 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012466 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.0 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864100755359 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000672231 0.001022116 -0.000662176 + 2 C : 0.000169023 -0.001077233 0.000373617 + 3 C : -0.000349312 -0.000525498 -0.000269710 + 4 H : -0.001224646 0.000009720 0.000404054 + 5 H : 0.000099024 0.000215680 0.000219024 + 6 H : 0.000199211 -0.000261306 -0.000265692 + 7 H : -0.000034004 0.000185485 0.000650409 + 8 H : 0.000596357 0.000559250 0.000233445 + 9 H : -0.000132860 -0.000117803 -0.000686446 + 10 H : 0.000004979 -0.000010411 0.000003475 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000386916 -0.0000318141 -0.0000177509 + +Norm of the Cartesian gradient ... 0.0027138408 +RMS gradient ... 0.0004954773 +MAX gradient ... 0.0012246462 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.651 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.116 sec ( 17.8%) +COSX gradient .... 0.412 sec ( 63.3%) +XC gradient .... 0.118 sec ( 18.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864100755 Eh +Current gradient norm .... 0.002713841 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124724863 0.000927841 0.027981578 0.042206131 0.052637336 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12472486 and components: + 1. -0.00329875 + 2. -0.04860968 + 3. -0.55527737 + 4. 0.51888315 + 5. 0.01022107 + 6. 0.01338854 + 7. 0.00011929 + 8. 0.00674682 + 9. -0.00155704 + 10. 0.00817106 + 11. 0.29872465 + 12. -0.01842229 + 13. -0.00387343 + 14. 0.00958091 + 15. -0.07010667 + 16. -0.01704238 + 17. -0.31181955 + 18. -0.03271644 + 19. 0.04635712 + 20. -0.03144318 + 21. 0.06043544 + 22. 0.09294042 + 23. -0.00536058 + 24. 0.02169064 + 25. -0.00855097 + 26. -0.01347882 + 27. -0.00219786 + 28. 0.00777009 + 29. 0.01309490 + 30. 0.10068491 + 31. -0.15563401 + 32. 0.14356802 + 33. 0.06185796 + 34. -0.11680706 + 35. -0.03882695 + 36. 0.16331904 + 37. -0.01197196 + 38. -0.17237557 + 39. 0.15534944 + 40. -0.00400236 + 41. -0.16440597 + 42. 0.10857281 + 43. -0.09025158 + 44. 0.06777552 + 45. -0.06214578 + +Lambda that maximizes along the TS mode: 0.00000533 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00064561 step = 0.00064561 +In cycle 2: lambdaN = -0.00097591 step = 0.00033031 +In cycle 3: lambdaN = -0.00100472 step = 0.00002881 +In cycle 4: lambdaN = -0.00100487 step = 0.00000015 +In cycle 5: lambdaN = -0.00100487 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00100487 +Calculated stepsize too large ( 0.7126 > 0.1000). Scaled with 0.1403. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0202523968 RMS(Int)= 0.0148954390 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000134304 +Previously predicted energy change .... 0.001803016 +Actually observed energy change .... -0.000146044 +Ratio of predicted to observed change .... 0.080999701 +New trust radius .... 0.100000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001460437 0.0000050000 NO + RMS gradient 0.0003468115 0.0001000000 NO + MAX gradient 0.0007457995 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0420996105 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0006 Max(Angles) 0.27 + Max(Dihed) 2.41 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5263 -0.000742 0.0003 1.5266 + 2. B(C 2,C 1) 1.5312 0.000116 -0.0004 1.5307 + 3. B(H 3,C 0) 1.3347 -0.000389 -0.0006 1.3342 0.56 + 4. B(H 3,C 1) 1.3171 0.000746 0.0002 1.3172 0.52 + 5. B(H 4,C 0) 1.0928 -0.000155 0.0000 1.0928 + 6. B(H 5,C 0) 1.0933 -0.000132 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0965 -0.000189 0.0001 1.0966 + 8. B(H 7,C 2) 1.1030 -0.000041 -0.0001 1.1029 + 9. B(H 8,C 2) 1.1012 -0.000116 0.0001 1.1014 + 10. B(H 9,C 2) 1.1056 0.000005 0.0001 1.1057 + 11. A(C 1,C 0,H 3) 54.32 0.000547 0.01 54.33 0.30 + 12. A(C 1,C 0,H 5) 119.12 -0.000079 -0.07 119.05 + 13. A(H 3,C 0,H 4) 113.55 -0.000180 0.22 113.77 + 14. A(C 1,C 0,H 4) 118.19 -0.000114 0.09 118.28 + 15. A(H 4,C 0,H 5) 118.45 0.000082 -0.02 118.43 + 16. A(H 3,C 0,H 5) 116.71 -0.000048 -0.21 116.50 + 17. A(C 0,C 1,H 3) 55.41 -0.000089 -0.04 55.37 0.31 + 18. A(H 3,C 1,H 6) 110.63 -0.000303 0.23 110.86 + 19. A(C 2,C 1,H 6) 118.00 -0.000264 0.04 118.05 + 20. A(C 0,C 1,H 6) 115.36 -0.000270 0.09 115.45 + 21. A(C 0,C 1,C 2) 121.25 0.000497 -0.10 121.15 + 22. A(C 2,C 1,H 3) 120.79 0.000559 -0.27 120.53 + 23. A(C 1,C 2,H 8) 110.53 -0.000158 0.08 110.61 + 24. A(C 1,C 2,H 7) 111.54 0.000357 -0.11 111.42 + 25. A(H 7,C 2,H 9) 107.49 -0.000045 -0.00 107.49 + 26. A(C 1,C 2,H 9) 111.38 -0.000016 0.00 111.39 + 27. A(H 7,C 2,H 8) 107.91 -0.000126 0.05 107.96 + 28. A(H 8,C 2,H 9) 107.83 -0.000024 -0.01 107.82 + 29. A(C 0,H 3,C 1) 70.27 -0.000458 0.03 70.30 + 30. D(H 3,C 1,C 0,H 5) 103.50 0.000204 -0.22 103.28 + 31. D(C 2,C 1,C 0,H 4) 8.02 0.000352 -0.54 7.47 + 32. D(H 6,C 1,C 0,H 3) -98.44 0.000250 -0.22 -98.66 + 33. D(C 2,C 1,C 0,H 5) -148.50 0.000623 -0.53 -149.03 + 34. D(H 3,C 1,C 0,H 4) -99.98 -0.000067 -0.24 -100.21 + 35. D(C 2,C 1,C 0,H 3) 107.99 0.000419 -0.31 107.69 + 36. D(H 7,C 2,C 1,C 0) -58.23 -0.000668 2.41 -55.82 + 37. D(H 8,C 2,C 1,H 6) 28.83 -0.000471 2.27 31.10 + 38. D(H 8,C 2,C 1,H 3) -112.58 -0.000337 2.19 -110.39 + 39. D(H 8,C 2,C 1,C 0) -178.28 -0.000639 2.38 -175.90 + 40. D(H 7,C 2,C 1,H 6) 148.88 -0.000500 2.31 151.19 + 41. D(H 7,C 2,C 1,H 3) 7.47 -0.000366 2.22 9.70 + 42. D(C 0,H 3,C 1,C 2) -108.82 -0.000305 0.00 -108.82 + 43. D(C 1,H 3,C 0,H 5) -108.02 -0.000090 -0.04 -108.05 + 44. D(C 1,H 3,C 0,H 4) 108.75 0.000086 -0.02 108.72 + 45. D(C 0,H 3,C 1,H 6) 107.23 -0.000164 -0.03 107.20 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s ( 5.969 %) +Internal coordinates : 0.000 s ( 0.479 %) +B/P matrices and projection : 0.000 s ( 4.097 %) +Hessian update/contruction : 0.000 s ( 4.323 %) +Making the step : 0.001 s ( 5.463 %) +Converting the step to Cartesian: 0.000 s ( 0.724 %) +Storing new data : 0.000 s ( 0.461 %) +Checking convergence : 0.000 s ( 0.190 %) +Final printing : 0.009 s (78.258 %) +Total time : 0.011 s + +Time for energy+gradient : 5.558 s +Time for complete geometry iter : 6.413 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 8 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.411026 -0.061553 0.050346 + C -0.020833 0.548859 -0.108458 + C 1.238410 -0.317689 -0.027694 + H -0.792221 0.708168 0.947330 + H -1.484926 -1.110857 0.346553 + H -2.252796 0.389639 -0.481780 + H 0.024409 1.470079 -0.701603 + H 1.280324 -0.880052 0.920080 + H 2.143398 0.306668 -0.092318 + H 1.275260 -1.053262 -0.852457 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.666452 -0.116318 0.095140 + 1 C 6.0000 0 12.011 -0.039369 1.037194 -0.204956 + 2 C 6.0000 0 12.011 2.340255 -0.600345 -0.052333 + 3 H 1.0000 0 1.008 -1.497080 1.338244 1.790195 + 4 H 1.0000 0 1.008 -2.806103 -2.099216 0.654890 + 5 H 1.0000 0 1.008 -4.257167 0.736311 -0.910432 + 6 H 1.0000 0 1.008 0.046127 2.778046 -1.325837 + 7 H 1.0000 0 1.008 2.419462 -1.663058 1.738700 + 8 H 1.0000 0 1.008 4.050435 0.579518 -0.174455 + 9 H 1.0000 0 1.008 2.409891 -1.990376 -1.610911 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526583629573 0.00000000 0.00000000 + C 2 1 0 1.530725518099 121.15118776 0.00000000 + H 2 1 3 1.317234505186 55.36754482 252.31287303 + H 1 2 3 1.092812347287 118.27564870 7.47361198 + H 1 2 3 1.093302109677 119.04517328 210.96651596 + H 2 1 3 1.096591431813 115.45150068 153.65259614 + H 3 2 1 1.102853044458 111.42441951 304.18622316 + H 3 2 1 1.101363399947 110.60655586 184.09866567 + H 3 2 1 1.105739769680 111.38604982 64.21100279 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.884824980421 0.00000000 0.00000000 + C 2 1 0 2.892652015412 121.15118776 0.00000000 + H 2 1 3 2.489212468953 55.36754482 252.31287303 + H 1 2 3 2.065116052139 118.27564870 7.47361198 + H 1 2 3 2.066041568928 119.04517328 210.96651596 + H 2 1 3 2.072257486932 115.45150068 153.65259614 + H 3 2 1 2.084090219987 111.42441951 304.18622316 + H 3 2 1 2.081275199824 110.60655586 184.09866567 + H 3 2 1 2.089545340080 111.38604982 64.21100279 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.816596740272 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.242e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40941 +Total number of batches ... 644 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5293 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 529 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10966 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24044 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2404 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8640015127655687 0.00e+00 7.29e-04 5.61e-03 8.01e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8641844704659860 -1.83e-04 3.67e-04 2.33e-03 1.04e-03 0.1 + 3 -116.8642093713788057 -2.49e-05 7.52e-05 3.75e-04 2.23e-04 0.1 + 4 -116.8642100210165751 -6.50e-07 2.44e-05 1.55e-04 6.02e-05 0.1 + 5 -116.8642100332787805 -1.23e-08 9.41e-06 5.40e-05 4.92e-05 0.1 + 6 -116.8642100550106733 -2.17e-08 1.97e-06 1.48e-05 4.63e-06 0.1 + 7 -116.8642100556330234 -6.22e-10 1.25e-06 1.04e-05 2.13e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.604511593 Eh +New exchange energy : -3.604537239 Eh +Exchange energy change after final integration : -0.000025646 Eh +Total energy after final integration : -116.864235702 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86423570180305 Eh -3180.03752 eV + +Components: +Nuclear Repulsion : 74.81659674027175 Eh 2035.86310 eV +Electronic Energy : -191.68080679590477 Eh -5215.89992 eV +One Electron Energy: -304.67486139505934 Eh -8290.62447 eV +Two Electron Energy: 112.99405459915457 Eh 3074.72454 eV + +Virial components: +Potential Energy : -232.18068650529449 Eh -6317.95768 eV +Kinetic Energy : 115.31645080349145 Eh 3137.92016 eV +Virial Ratio : 2.01342206500050 + +DFT components: +N(Alpha) : 13.000000308006 electrons +N(Beta) : 11.999999756854 electrons +N(Total) : 25.000000064860 electrons +E(X) : -14.252655772986 Eh +E(C) : -0.919800936144 Eh +E(XC) : -15.172456709131 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.2235e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.0399e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.2465e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9718e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.1279e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.6999e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762451 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012451 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.1 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864235701803 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000692445 0.000771740 -0.000556150 + 2 C : 0.000157023 -0.000821400 0.000365068 + 3 C : -0.000394620 -0.000545615 -0.000239571 + 4 H : -0.001053342 0.000041675 0.000329423 + 5 H : 0.000008876 0.000170236 0.000136569 + 6 H : 0.000167227 -0.000218920 -0.000226514 + 7 H : -0.000015952 0.000184594 0.000586156 + 8 H : 0.000537904 0.000527221 0.000253336 + 9 H : -0.000115371 -0.000091346 -0.000649960 + 10 H : 0.000015809 -0.000018186 0.000001642 + +Difference to translation invariance: + : 0.0000000000 -0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000287606 -0.0000338440 -0.0000170613 + +Norm of the Cartesian gradient ... 0.0023614788 +RMS gradient ... 0.0004311451 +MAX gradient ... 0.0010533416 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.665 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.7%) +RI-J Coulomb gradient .... 0.116 sec ( 17.5%) +COSX gradient .... 0.423 sec ( 63.6%) +XC gradient .... 0.120 sec ( 18.1%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864235702 Eh +Current gradient norm .... 0.002361479 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.100 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124731546 0.001035556 0.027984415 0.042214927 0.052638536 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473155 and components: + 1. -0.00328740 + 2. -0.04862298 + 3. -0.55529509 + 4. 0.51888377 + 5. 0.01021991 + 6. 0.01338702 + 7. 0.00012008 + 8. 0.00673981 + 9. -0.00155063 + 10. 0.00817454 + 11. 0.29872460 + 12. -0.01844700 + 13. -0.00379871 + 14. 0.00960186 + 15. -0.07010093 + 16. -0.01712435 + 17. -0.31182998 + 18. -0.03262123 + 19. 0.04636823 + 20. -0.03140669 + 21. 0.06040184 + 22. 0.09282687 + 23. -0.00532106 + 24. 0.02164447 + 25. -0.00855123 + 26. -0.01348413 + 27. -0.00217831 + 28. 0.00776349 + 29. 0.01310538 + 30. 0.10059441 + 31. -0.15584996 + 32. 0.14347289 + 33. 0.06163566 + 34. -0.11689121 + 35. -0.03895875 + 36. 0.16439738 + 37. -0.01095735 + 38. -0.17138492 + 39. 0.15640765 + 40. -0.00296762 + 41. -0.16339519 + 42. 0.10855647 + 43. -0.09026883 + 44. 0.06775724 + 45. -0.06216148 + +Lambda that maximizes along the TS mode: 0.00000356 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00062881 step = 0.00062881 +In cycle 2: lambdaN = -0.00085454 step = 0.00022573 +In cycle 3: lambdaN = -0.00086535 step = 0.00001081 +In cycle 4: lambdaN = -0.00086537 step = 0.00000002 +In cycle 5: lambdaN = -0.00086537 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00086537 +Calculated stepsize too large ( 0.6682 > 0.1000). Scaled with 0.1496. +The final length of the internal step .... 0.1000 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0149071198 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0203143365 RMS(Int)= 0.0148959406 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000123645 +Previously predicted energy change .... -0.000134304 +Actually observed energy change .... -0.000134946 +Ratio of predicted to observed change .... 1.004781057 +New trust radius .... 0.150000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001349464 0.0000050000 NO + RMS gradient 0.0003021625 0.0001000000 NO + MAX gradient 0.0006514244 0.0003000000 NO + RMS step 0.0149071198 0.0020000000 NO + MAX step 0.0422301968 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0005 Max(Angles) 0.26 + Max(Dihed) 2.42 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5266 -0.000651 0.0003 1.5269 + 2. B(C 2,C 1) 1.5307 0.000074 -0.0004 1.5303 + 3. B(H 3,C 0) 1.3342 -0.000302 -0.0005 1.3336 0.56 + 4. B(H 3,C 1) 1.3172 0.000618 0.0001 1.3173 0.52 + 5. B(H 4,C 0) 1.0928 -0.000126 0.0000 1.0928 + 6. B(H 5,C 0) 1.0933 -0.000110 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0966 -0.000162 0.0000 1.0966 + 8. B(H 7,C 2) 1.1029 -0.000031 -0.0001 1.1027 + 9. B(H 8,C 2) 1.1014 -0.000108 0.0001 1.1015 + 10. B(H 9,C 2) 1.1057 0.000012 0.0001 1.1058 + 11. A(C 1,C 0,H 3) 54.33 0.000459 0.00 54.33 0.30 + 12. A(C 1,C 0,H 5) 119.05 -0.000086 -0.07 118.98 + 13. A(H 3,C 0,H 4) 113.77 -0.000097 0.19 113.97 + 14. A(C 1,C 0,H 4) 118.28 -0.000040 0.08 118.35 + 15. A(H 4,C 0,H 5) 118.43 0.000028 -0.01 118.42 + 16. A(H 3,C 0,H 5) 116.50 -0.000059 -0.19 116.31 + 17. A(C 0,C 1,H 3) 55.37 -0.000056 -0.03 55.33 0.31 + 18. A(H 3,C 1,H 6) 110.86 -0.000261 0.22 111.08 + 19. A(C 2,C 1,H 6) 118.05 -0.000217 0.04 118.08 + 20. A(C 0,C 1,H 6) 115.45 -0.000228 0.09 115.54 + 21. A(C 0,C 1,C 2) 121.15 0.000403 -0.09 121.06 + 22. A(C 2,C 1,H 3) 120.53 0.000475 -0.26 120.26 + 23. A(C 1,C 2,H 8) 110.61 -0.000156 0.08 110.69 + 24. A(C 1,C 2,H 7) 111.42 0.000302 -0.11 111.31 + 25. A(H 7,C 2,H 9) 107.49 -0.000039 -0.00 107.49 + 26. A(C 1,C 2,H 9) 111.39 0.000010 -0.00 111.38 + 27. A(H 7,C 2,H 8) 107.95 -0.000104 0.05 108.00 + 28. A(H 8,C 2,H 9) 107.82 -0.000023 -0.02 107.80 + 29. A(C 0,H 3,C 1) 70.30 -0.000404 0.03 70.33 + 30. D(H 3,C 1,C 0,H 5) 103.28 0.000160 -0.21 103.07 + 31. D(C 2,C 1,C 0,H 4) 7.47 0.000282 -0.51 6.97 + 32. D(H 6,C 1,C 0,H 3) -98.66 0.000210 -0.21 -98.87 + 33. D(C 2,C 1,C 0,H 5) -149.03 0.000532 -0.51 -149.54 + 34. D(H 3,C 1,C 0,H 4) -100.21 -0.000090 -0.21 -100.42 + 35. D(C 2,C 1,C 0,H 3) 107.69 0.000373 -0.30 107.39 + 36. D(H 7,C 2,C 1,C 0) -55.81 -0.000629 2.42 -53.39 + 37. D(H 8,C 2,C 1,H 6) 31.10 -0.000430 2.27 33.37 + 38. D(H 8,C 2,C 1,H 3) -110.39 -0.000323 2.20 -108.19 + 39. D(H 8,C 2,C 1,C 0) -175.90 -0.000593 2.38 -173.52 + 40. D(H 7,C 2,C 1,H 6) 151.19 -0.000466 2.31 153.50 + 41. D(H 7,C 2,C 1,H 3) 9.70 -0.000359 2.24 11.94 + 42. D(C 0,H 3,C 1,C 2) -108.82 -0.000241 -0.01 -108.83 + 43. D(C 1,H 3,C 0,H 5) -108.05 -0.000060 -0.03 -108.08 + 44. D(C 1,H 3,C 0,H 4) 108.72 0.000112 -0.02 108.70 + 45. D(C 0,H 3,C 1,H 6) 107.20 -0.000132 -0.03 107.17 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s ( 5.816 %) +Internal coordinates : 0.000 s ( 0.452 %) +B/P matrices and projection : 0.001 s (12.997 %) +Hessian update/contruction : 0.000 s ( 4.422 %) +Making the step : 0.001 s ( 5.308 %) +Converting the step to Cartesian: 0.000 s ( 0.628 %) +Storing new data : 0.000 s ( 0.554 %) +Checking convergence : 0.000 s ( 0.185 %) +Final printing : 0.008 s (69.611 %) +Total time : 0.011 s + +Time for energy+gradient : 5.694 s +Time for complete geometry iter : 6.592 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 9 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.410073 -0.061466 0.057199 + C -0.021060 0.548281 -0.116620 + C 1.237849 -0.317382 -0.028757 + H -0.786162 0.716777 0.942429 + H -1.482853 -1.108835 0.360518 + H -2.255408 0.387126 -0.471454 + H 0.021905 1.461977 -0.721542 + H 1.260464 -0.897947 0.908495 + H 2.143649 0.308392 -0.063507 + H 1.291690 -1.036923 -0.866760 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.664653 -0.116154 0.108090 + 1 C 6.0000 0 12.011 -0.039798 1.036100 -0.220380 + 2 C 6.0000 0 12.011 2.339196 -0.599764 -0.054343 + 3 H 1.0000 0 1.008 -1.485630 1.354513 1.780932 + 4 H 1.0000 0 1.008 -2.802187 -2.095395 0.681281 + 5 H 1.0000 0 1.008 -4.262104 0.731561 -0.890919 + 6 H 1.0000 0 1.008 0.041394 2.762736 -1.363517 + 7 H 1.0000 0 1.008 2.381932 -1.696873 1.716807 + 8 H 1.0000 0 1.008 4.050910 0.582776 -0.120011 + 9 H 1.0000 0 1.008 2.440941 -1.959500 -1.637940 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.526879534308 0.00000000 0.00000000 + C 2 1 0 1.530341034089 121.05931857 0.00000000 + H 2 1 3 1.317328991069 55.33366245 252.61450569 + H 1 2 3 1.092832377802 118.35345351 6.96642478 + H 1 2 3 1.093297678278 118.97862400 210.45917510 + H 2 1 3 1.096639152563 115.54118482 153.74617525 + H 3 2 1 1.102727865331 111.31417748 306.60566121 + H 3 2 1 1.101486837369 110.68996421 186.47542547 + H 3 2 1 1.105842498934 111.38342932 66.55294338 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.885384159331 0.00000000 0.00000000 + C 2 1 0 2.891925445930 121.05931857 0.00000000 + H 2 1 3 2.489391021395 55.33366245 252.61450569 + H 1 2 3 2.065153904328 118.35345351 6.96642478 + H 1 2 3 2.066033194797 118.97862400 210.45917510 + H 2 1 3 2.072347666079 115.54118482 153.74617525 + H 3 2 1 2.083853665719 111.31417748 306.60566121 + H 3 2 1 2.081508462747 110.68996421 186.47542547 + H 3 2 1 2.089739470236 111.38342932 66.55294338 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.825672221532 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.242e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40943 +Total number of batches ... 646 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5294 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 529 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10962 +Total number of batches ... 90 +Average number of points per batch ... 121 +Average number of grid points per atom ... 1096 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24045 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2404 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8641230023553845 0.00e+00 7.30e-04 5.63e-03 8.16e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8643065993575902 -1.84e-04 3.67e-04 2.34e-03 1.06e-03 0.1 + 3 -116.8643315115832166 -2.49e-05 7.44e-05 3.70e-04 2.17e-04 0.1 + 4 -116.8643321522217065 -6.41e-07 2.29e-05 1.45e-04 5.55e-05 0.1 + 5 -116.8643321641230131 -1.19e-08 8.86e-06 5.36e-05 4.71e-05 0.1 + 6 -116.8643321834165789 -1.93e-08 1.83e-06 1.42e-05 4.61e-06 0.1 + 7 -116.8643321842814231 -8.65e-10 1.19e-06 1.00e-05 2.02e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 7 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.101 sec) +Old exchange energy : -3.604510496 Eh +New exchange energy : -3.604537130 Eh +Exchange energy change after final integration : -0.000026634 Eh +Total energy after final integration : -116.864358818 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86435881822055 Eh -3180.04087 eV + +Components: +Nuclear Repulsion : 74.82567222153237 Eh 2036.11005 eV +Electronic Energy : -191.69000440581380 Eh -5216.15020 eV +One Electron Energy: -304.69247002415398 Eh -8291.10362 eV +Two Electron Energy: 113.00246561834018 Eh 3074.95342 eV + +Virial components: +Potential Energy : -232.18055228755480 Eh -6317.95403 eV +Kinetic Energy : 115.31619346933425 Eh 3137.91315 eV +Virial Ratio : 2.01342539414725 + +DFT components: +N(Alpha) : 12.999998344984 electrons +N(Beta) : 11.999997599612 electrons +N(Total) : 24.999995944596 electrons +E(X) : -14.252640316568 Eh +E(C) : -0.919808777256 Eh +E(XC) : -15.172449093824 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 8.6484e-10 Tolerance : 1.0000e-08 + Last MAX-Density change ... 9.9984e-06 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.1921e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.9690e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.0180e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 9.3213e-06 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762434 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012434 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.1 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.2 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864358818221 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000702540 0.000541783 -0.000428442 + 2 C : 0.000159385 -0.000574214 0.000314850 + 3 C : -0.000414425 -0.000543125 -0.000194655 + 4 H : -0.000926268 0.000044524 0.000259735 + 5 H : -0.000061056 0.000136153 0.000073337 + 6 H : 0.000142569 -0.000169756 -0.000190023 + 7 H : 0.000003240 0.000173876 0.000519114 + 8 H : 0.000470901 0.000484527 0.000255769 + 9 H : -0.000097104 -0.000068969 -0.000609880 + 10 H : 0.000020218 -0.000024799 0.000000194 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : 0.0000146583 -0.0000252600 -0.0000174210 + +Norm of the Cartesian gradient ... 0.0020441783 +RMS gradient ... 0.0003732142 +MAX gradient ... 0.0009262682 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.646 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 18.1%) +COSX gradient .... 0.402 sec ( 62.1%) +XC gradient .... 0.122 sec ( 18.9%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864358818 Eh +Current gradient norm .... 0.002044178 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.150 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124731251 0.001151393 0.027985337 0.042223145 0.052638825 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473125 and components: + 1. -0.00328688 + 2. -0.04861832 + 3. -0.55529678 + 4. 0.51888534 + 5. 0.01021985 + 6. 0.01338670 + 7. 0.00012034 + 8. 0.00674062 + 9. -0.00154980 + 10. 0.00817297 + 11. 0.29872537 + 12. -0.01843916 + 13. -0.00381743 + 14. 0.00958793 + 15. -0.07009467 + 16. -0.01711119 + 17. -0.31183106 + 18. -0.03263090 + 19. 0.04636529 + 20. -0.03141212 + 21. 0.06041180 + 22. 0.09283606 + 23. -0.00532144 + 24. 0.02164944 + 25. -0.00855070 + 26. -0.01348731 + 27. -0.00218081 + 28. 0.00776382 + 29. 0.01310569 + 30. 0.10060707 + 31. -0.15582870 + 32. 0.14348205 + 33. 0.06165463 + 34. -0.11687627 + 35. -0.03895244 + 36. 0.16433581 + 37. -0.01102073 + 38. -0.17143890 + 39. 0.15634663 + 40. -0.00303155 + 41. -0.16344971 + 42. 0.10854800 + 43. -0.09027179 + 44. 0.06775139 + 45. -0.06216218 + +Lambda that maximizes along the TS mode: 0.00000259 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00058100 step = 0.00058100 +In cycle 2: lambdaN = -0.00071590 step = 0.00013490 +In cycle 3: lambdaN = -0.00071901 step = 0.00000311 +In cycle 4: lambdaN = -0.00071901 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00071901 +Calculated stepsize too large ( 0.6150 > 0.1500). Scaled with 0.2439. +The final length of the internal step .... 0.1500 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0223606798 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0305427065 RMS(Int)= 0.0223348030 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000161511 +Previously predicted energy change .... -0.000123645 +Actually observed energy change .... -0.000123116 +Ratio of predicted to observed change .... 0.995728260 +New trust radius .... 0.225000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001231164 0.0000050000 NO + RMS gradient 0.0002615475 0.0001000000 NO + MAX gradient 0.0005710710 0.0003000000 NO + RMS step 0.0223606798 0.0020000000 NO + MAX step 0.0634849241 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0008 Max(Angles) 0.38 + Max(Dihed) 3.64 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5269 -0.000561 0.0004 1.5273 + 2. B(C 2,C 1) 1.5303 0.000037 -0.0005 1.5298 + 3. B(H 3,C 0) 1.3336 -0.000248 -0.0008 1.3328 0.56 + 4. B(H 3,C 1) 1.3173 0.000521 0.0002 1.3175 0.52 + 5. B(H 4,C 0) 1.0928 -0.000105 0.0000 1.0929 + 6. B(H 5,C 0) 1.0933 -0.000089 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0966 -0.000141 0.0001 1.0967 + 8. B(H 7,C 2) 1.1027 -0.000029 -0.0002 1.1025 + 9. B(H 8,C 2) 1.1015 -0.000099 0.0002 1.1017 + 10. B(H 9,C 2) 1.1058 0.000017 0.0001 1.1060 + 11. A(C 1,C 0,H 3) 54.33 0.000389 0.01 54.34 0.30 + 12. A(C 1,C 0,H 5) 118.98 -0.000097 -0.09 118.89 + 13. A(H 3,C 0,H 4) 113.97 -0.000034 0.26 114.22 + 14. A(C 1,C 0,H 4) 118.35 0.000020 0.10 118.45 + 15. A(H 4,C 0,H 5) 118.42 -0.000008 -0.00 118.42 + 16. A(H 3,C 0,H 5) 116.31 -0.000074 -0.26 116.05 + 17. A(C 0,C 1,H 3) 55.33 -0.000041 -0.05 55.28 0.31 + 18. A(H 3,C 1,H 6) 111.08 -0.000215 0.31 111.39 + 19. A(C 2,C 1,H 6) 118.08 -0.000174 0.05 118.13 + 20. A(C 0,C 1,H 6) 115.54 -0.000182 0.13 115.67 + 21. A(C 0,C 1,C 2) 121.06 0.000314 -0.12 120.94 + 22. A(C 2,C 1,H 3) 120.26 0.000397 -0.38 119.88 + 23. A(C 1,C 2,H 8) 110.69 -0.000145 0.13 110.82 + 24. A(C 1,C 2,H 7) 111.31 0.000248 -0.16 111.15 + 25. A(H 7,C 2,H 9) 107.49 -0.000037 -0.00 107.49 + 26. A(C 1,C 2,H 9) 111.38 0.000025 -0.01 111.37 + 27. A(H 7,C 2,H 8) 108.00 -0.000080 0.07 108.07 + 28. A(H 8,C 2,H 9) 107.80 -0.000020 -0.02 107.78 + 29. A(C 0,H 3,C 1) 70.33 -0.000348 0.04 70.38 + 30. D(H 3,C 1,C 0,H 5) 103.07 0.000120 -0.28 102.80 + 31. D(C 2,C 1,C 0,H 4) 6.97 0.000220 -0.72 6.24 + 32. D(H 6,C 1,C 0,H 3) -98.87 0.000175 -0.29 -99.16 + 33. D(C 2,C 1,C 0,H 5) -149.54 0.000445 -0.73 -150.27 + 34. D(H 3,C 1,C 0,H 4) -100.42 -0.000105 -0.28 -100.69 + 35. D(C 2,C 1,C 0,H 3) 107.39 0.000325 -0.45 106.94 + 36. D(H 7,C 2,C 1,C 0) -53.39 -0.000571 3.64 -49.76 + 37. D(H 8,C 2,C 1,H 6) 33.37 -0.000387 3.39 36.76 + 38. D(H 8,C 2,C 1,H 3) -108.19 -0.000317 3.32 -104.88 + 39. D(H 8,C 2,C 1,C 0) -173.52 -0.000538 3.57 -169.95 + 40. D(H 7,C 2,C 1,H 6) 153.50 -0.000420 3.46 156.96 + 41. D(H 7,C 2,C 1,H 3) 11.94 -0.000349 3.38 15.32 + 42. D(C 0,H 3,C 1,C 2) -108.83 -0.000173 -0.03 -108.86 + 43. D(C 1,H 3,C 0,H 5) -108.08 -0.000032 -0.04 -108.12 + 44. D(C 1,H 3,C 0,H 4) 108.70 0.000134 -0.03 108.67 + 45. D(C 0,H 3,C 1,H 6) 107.17 -0.000101 -0.04 107.14 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (18.970 %) +Internal coordinates : 0.000 s ( 1.475 %) +B/P matrices and projection : 0.000 s (13.731 %) +Hessian update/contruction : 0.000 s (12.376 %) +Making the step : 0.001 s (17.314 %) +Converting the step to Cartesian: 0.000 s ( 1.897 %) +Storing new data : 0.000 s ( 1.295 %) +Checking convergence : 0.000 s ( 0.572 %) +Final printing : 0.001 s (32.310 %) +Total time : 0.003 s + +Time for energy+gradient : 5.603 s +Time for complete geometry iter : 6.428 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 10 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.408771 -0.061040 0.067436 + C -0.021534 0.547026 -0.128835 + C 1.237088 -0.316992 -0.030359 + H -0.777232 0.729643 0.934839 + H -1.479766 -1.105234 0.382013 + H -2.259227 0.383510 -0.456367 + H 0.018026 1.449308 -0.751004 + H 1.231548 -0.924693 0.889574 + H 2.142750 0.310214 -0.020141 + H 1.317118 -1.011741 -0.887156 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.662191 -0.115348 0.127436 + 1 C 6.0000 0 12.011 -0.040694 1.033728 -0.243462 + 2 C 6.0000 0 12.011 2.337758 -0.599027 -0.057370 + 3 H 1.0000 0 1.008 -1.468755 1.378825 1.766590 + 4 H 1.0000 0 1.008 -2.796353 -2.088590 0.721900 + 5 H 1.0000 0 1.008 -4.269320 0.724729 -0.862409 + 6 H 1.0000 0 1.008 0.034064 2.738795 -1.419192 + 7 H 1.0000 0 1.008 2.327289 -1.747416 1.681051 + 8 H 1.0000 0 1.008 4.049211 0.586219 -0.038061 + 9 H 1.0000 0 1.008 2.488992 -1.911914 -1.676482 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.527315001651 0.00000000 0.00000000 + C 2 1 0 1.529821616340 120.94005990 0.00000000 + H 2 1 3 1.317508678039 55.28188805 253.06227976 + H 1 2 3 1.092859279824 118.45014580 6.24346597 + H 1 2 3 1.093284087033 118.88750394 209.73395623 + H 2 1 3 1.096710381275 115.67157893 153.90259712 + H 3 2 1 1.102546285048 111.15374770 310.24293637 + H 3 2 1 1.101686751051 110.81762550 190.04749352 + H 3 2 1 1.105975756601 111.37370076 70.07497461 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.886207073350 0.00000000 0.00000000 + C 2 1 0 2.890943888636 120.94005990 0.00000000 + H 2 1 3 2.489730580558 55.28188805 253.06227976 + H 1 2 3 2.065204741782 118.45014580 6.24346597 + H 1 2 3 2.066007511067 118.88750394 209.73395623 + H 2 1 3 2.072482268838 115.67157893 153.90259712 + H 3 2 1 2.083510528713 111.15374770 310.24293637 + H 3 2 1 2.081886244855 110.81762550 190.04749352 + H 3 2 1 2.089991290732 111.37370076 70.07497461 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.837873533087 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.242e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40952 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5300 +Total number of batches ... 47 +Average number of points per batch ... 112 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10974 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24046 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2405 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.8640216649829284 0.00e+00 3.29e-04 2.54e-03 4.45e-03 0.700 0.1 + 2 -116.8641408140031928 -1.19e-04 3.25e-04 2.44e-03 3.52e-03 0.700 0.1 + ***Turning on AO-DIIS*** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 3 -116.8642373265824261 -9.65e-05 9.46e-04 6.87e-03 2.64e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 4 -116.8644910730998987 -2.54e-04 1.27e-04 7.01e-04 4.76e-04 0.1 + 5 -116.8644934700898972 -2.40e-06 7.55e-05 4.34e-04 1.38e-04 0.1 + 6 -116.8644935353405714 -6.53e-08 2.97e-05 1.50e-04 1.31e-04 0.1 + 7 -116.8644937176696175 -1.82e-07 4.02e-06 3.21e-05 1.28e-05 0.1 + 8 -116.8644937195875713 -1.92e-09 3.06e-06 2.19e-05 5.07e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 8 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.604509868 Eh +New exchange energy : -3.604534984 Eh +Exchange energy change after final integration : -0.000025115 Eh +Total energy after final integration : -116.864518835 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86451883480143 Eh -3180.04523 eV + +Components: +Nuclear Repulsion : 74.83787353308698 Eh 2036.44207 eV +Electronic Energy : -191.70236725267455 Eh -5216.48661 eV +One Electron Energy: -304.71608761909602 Eh -8291.74629 eV +Two Electron Energy: 113.01372036642147 Eh 3075.25967 eV + +Virial components: +Potential Energy : -232.18036310189694 Eh -6317.94888 eV +Kinetic Energy : 115.31584426709553 Eh 3137.90365 eV +Virial Ratio : 2.01342985066405 + +DFT components: +N(Alpha) : 12.999997044674 electrons +N(Beta) : 11.999995969139 electrons +N(Total) : 24.999993013813 electrons +E(X) : -14.252613329389 Eh +E(C) : -0.919820882193 Eh +E(XC) : -15.172434211581 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 1.9180e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.1909e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.0612e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.6391e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 5.0699e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.4179e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762410 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012410 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.3 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864518834801 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000682453 0.000213305 -0.000260199 + 2 C : 0.000143362 -0.000234474 0.000249763 + 3 C : -0.000406559 -0.000502172 -0.000117820 + 4 H : -0.000722506 0.000052562 0.000161991 + 5 H : -0.000141859 0.000091190 0.000000956 + 6 H : 0.000116467 -0.000096310 -0.000135988 + 7 H : 0.000026975 0.000147051 0.000407662 + 8 H : 0.000353212 0.000402898 0.000239681 + 9 H : -0.000070836 -0.000035274 -0.000535953 + 10 H : 0.000019290 -0.000038775 -0.000010093 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000053936 -0.0000014556 -0.0000257296 + +Norm of the Cartesian gradient ... 0.0016116930 +RMS gradient ... 0.0002942535 +MAX gradient ... 0.0007225059 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.662 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.116 sec ( 17.6%) +COSX gradient .... 0.419 sec ( 63.3%) +XC gradient .... 0.121 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864518835 Eh +Current gradient norm .... 0.001611693 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.225 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124733199 0.001313620 0.027984404 0.042230649 0.052638960 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473320 and components: + 1. 0.00328297 + 2. 0.04861950 + 3. 0.55530380 + 4. -0.51888733 + 5. -0.01021966 + 6. -0.01338622 + 7. -0.00012085 + 8. -0.00673860 + 9. 0.00154688 + 10. -0.00817208 + 11. -0.29872623 + 12. 0.01844281 + 13. 0.00380206 + 14. -0.00958679 + 15. 0.07008930 + 16. 0.01713180 + 17. 0.31183529 + 18. 0.03260198 + 19. -0.04636586 + 20. 0.03140230 + 21. -0.06040985 + 22. -0.09279770 + 23. 0.00530627 + 24. -0.02163589 + 25. 0.00854994 + 26. 0.01349024 + 27. 0.00217684 + 28. -0.00776026 + 29. -0.01310906 + 30. -0.10058326 + 31. 0.15589974 + 32. -0.14345264 + 33. -0.06158092 + 34. 0.11689740 + 35. 0.03900234 + 36. -0.16474636 + 37. 0.01063916 + 38. 0.17105389 + 39. -0.15675141 + 40. 0.00264422 + 41. 0.16305894 + 42. -0.10852981 + 43. 0.09027977 + 44. -0.06774124 + 45. 0.06216851 + +Lambda that maximizes along the TS mode: 0.00000135 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00045540 step = 0.00045540 +In cycle 2: lambdaN = -0.00050299 step = 0.00004759 +In cycle 3: lambdaN = -0.00050327 step = 0.00000028 +In cycle 4: lambdaN = -0.00050327 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00050327 +Calculated stepsize too large ( 0.5230 > 0.2250). Scaled with 0.4302. +The final length of the internal step .... 0.2250 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0335410197 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0459073785 RMS(Int)= 0.0334803692 + Iter 5: RMS(Cart)= 0.0000000133 RMS(Int)= 0.0000000104 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000182210 +Previously predicted energy change .... -0.000161511 +Actually observed energy change .... -0.000160017 +Ratio of predicted to observed change .... 0.990745562 +New trust radius .... 0.337500000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001600166 0.0000050000 NO + RMS gradient 0.0002025419 0.0001000000 NO + MAX gradient 0.0004716925 0.0003000000 NO + RMS step 0.0335410197 0.0020000000 NO + MAX step 0.0953200225 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0011 Max(Angles) 0.56 + Max(Dihed) 5.46 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5273 -0.000432 0.0006 1.5279 + 2. B(C 2,C 1) 1.5298 -0.000017 -0.0007 1.5292 + 3. B(H 3,C 0) 1.3328 -0.000163 -0.0011 1.3317 0.56 + 4. B(H 3,C 1) 1.3175 0.000372 0.0003 1.3178 0.52 + 5. B(H 4,C 0) 1.0929 -0.000077 0.0000 1.0929 + 6. B(H 5,C 0) 1.0933 -0.000065 -0.0000 1.0933 + 7. B(H 6,C 1) 1.0967 -0.000109 0.0001 1.0968 + 8. B(H 7,C 2) 1.1025 -0.000024 -0.0003 1.1023 + 9. B(H 8,C 2) 1.1017 -0.000083 0.0003 1.1020 + 10. B(H 9,C 2) 1.1060 0.000033 0.0001 1.1061 + 11. A(C 1,C 0,H 3) 54.34 0.000284 0.01 54.36 0.30 + 12. A(C 1,C 0,H 5) 118.89 -0.000113 -0.12 118.77 + 13. A(H 3,C 0,H 4) 114.22 0.000044 0.33 114.55 + 14. A(C 1,C 0,H 4) 118.45 0.000093 0.11 118.56 + 15. A(H 4,C 0,H 5) 118.42 -0.000044 0.01 118.43 + 16. A(H 3,C 0,H 5) 116.05 -0.000093 -0.34 115.71 + 17. A(C 0,C 1,H 3) 55.28 -0.000015 -0.07 55.21 0.31 + 18. A(H 3,C 1,H 6) 111.39 -0.000147 0.43 111.81 + 19. A(C 2,C 1,H 6) 118.13 -0.000109 0.06 118.19 + 20. A(C 0,C 1,H 6) 115.67 -0.000113 0.19 115.86 + 21. A(C 0,C 1,C 2) 120.94 0.000178 -0.14 120.80 + 22. A(C 2,C 1,H 3) 119.88 0.000280 -0.56 119.33 + 23. A(C 1,C 2,H 8) 110.82 -0.000121 0.19 111.01 + 24. A(C 1,C 2,H 7) 111.15 0.000159 -0.23 110.93 + 25. A(H 7,C 2,H 9) 107.49 -0.000033 0.00 107.49 + 26. A(C 1,C 2,H 9) 111.37 0.000035 -0.02 111.36 + 27. A(H 7,C 2,H 8) 108.07 -0.000036 0.09 108.16 + 28. A(H 8,C 2,H 9) 107.78 -0.000007 -0.04 107.74 + 29. A(C 0,H 3,C 1) 70.38 -0.000268 0.06 70.43 + 30. D(H 3,C 1,C 0,H 5) 102.80 0.000063 -0.37 102.43 + 31. D(C 2,C 1,C 0,H 4) 6.24 0.000140 -1.03 5.22 + 32. D(H 6,C 1,C 0,H 3) -99.16 0.000122 -0.40 -99.56 + 33. D(C 2,C 1,C 0,H 5) -150.27 0.000321 -1.03 -151.30 + 34. D(H 3,C 1,C 0,H 4) -100.69 -0.000117 -0.36 -101.05 + 35. D(C 2,C 1,C 0,H 3) 106.94 0.000257 -0.67 106.27 + 36. D(H 7,C 2,C 1,C 0) -49.76 -0.000472 5.46 -44.30 + 37. D(H 8,C 2,C 1,H 6) 36.76 -0.000314 5.07 41.83 + 38. D(H 8,C 2,C 1,H 3) -104.88 -0.000296 5.02 -99.86 + 39. D(H 8,C 2,C 1,C 0) -169.95 -0.000451 5.37 -164.58 + 40. D(H 7,C 2,C 1,H 6) 156.96 -0.000335 5.16 162.12 + 41. D(H 7,C 2,C 1,H 3) 15.32 -0.000317 5.11 20.43 + 42. D(C 0,H 3,C 1,C 2) -108.86 -0.000070 -0.10 -108.96 + 43. D(C 1,H 3,C 0,H 5) -108.12 0.000009 -0.06 -108.18 + 44. D(C 1,H 3,C 0,H 4) 108.67 0.000155 -0.05 108.62 + 45. D(C 0,H 3,C 1,H 6) 107.14 -0.000053 -0.04 107.09 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s ( 5.849 %) +Internal coordinates : 0.000 s ( 0.432 %) +B/P matrices and projection : 0.000 s ( 4.111 %) +Hessian update/contruction : 0.000 s ( 3.853 %) +Making the step : 0.001 s ( 5.444 %) +Converting the step to Cartesian: 0.000 s ( 0.736 %) +Storing new data : 0.000 s ( 0.432 %) +Checking convergence : 0.000 s ( 0.175 %) +Final printing : 0.009 s (78.931 %) +Total time : 0.011 s + +Time for energy+gradient : 5.588 s +Time for complete geometry iter : 6.422 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 11 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.407101 -0.059798 0.082684 + C -0.022574 0.544248 -0.147071 + C 1.236103 -0.316576 -0.032758 + H -0.763998 0.748808 0.922960 + H -1.475365 -1.098695 0.415009 + H -2.264796 0.378640 -0.434373 + H 0.011906 1.429081 -0.794276 + H 1.190462 -0.964365 0.857920 + H 2.138436 0.311238 0.045013 + H 1.356929 -0.972581 -0.915109 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.659036 -0.113001 0.156250 + 1 C 6.0000 0 12.011 -0.042659 1.028480 -0.277924 + 2 C 6.0000 0 12.011 2.335896 -0.598243 -0.061904 + 3 H 1.0000 0 1.008 -1.443746 1.415042 1.744142 + 4 H 1.0000 0 1.008 -2.788036 -2.076233 0.784254 + 5 H 1.0000 0 1.008 -4.279845 0.715526 -0.820845 + 6 H 1.0000 0 1.008 0.022499 2.700572 -1.500963 + 7 H 1.0000 0 1.008 2.249646 -1.822386 1.621235 + 8 H 1.0000 0 1.008 4.041058 0.588154 0.085061 + 9 H 1.0000 0 1.008 2.564224 -1.837911 -1.729306 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.527930944803 0.00000000 0.00000000 + C 2 1 0 1.529167814434 120.80177199 0.00000000 + H 2 1 3 1.317771055017 55.21071049 253.73014267 + H 1 2 3 1.092889937594 118.56325669 5.21505136 + H 1 2 3 1.093259456392 118.76619639 208.69943353 + H 2 1 3 1.096810201806 115.85828892 154.16894758 + H 3 2 1 1.102280242258 110.92523044 315.70450342 + H 3 2 1 1.101999846442 111.01082017 195.41841954 + H 3 2 1 1.106112038957 111.35479066 75.37432216 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.887371037220 0.00000000 0.00000000 + C 2 1 0 2.889708382088 120.80177199 0.00000000 + H 2 1 3 2.490226401191 55.21071049 253.73014267 + H 1 2 3 2.065262676571 118.56325669 5.21505136 + H 1 2 3 2.065960965900 118.76619639 208.69943353 + H 2 1 3 2.072670902303 115.85828892 154.16894758 + H 3 2 1 2.083007780700 110.92523044 315.70450342 + H 3 2 1 2.082477909399 111.01082017 195.41841954 + H 3 2 1 2.090248827062 111.35479066 75.37432216 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.853144290524 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.241e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40944 +Total number of batches ... 647 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5299 +Total number of batches ... 47 +Average number of points per batch ... 112 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10980 +Total number of batches ... 90 +Average number of points per batch ... 122 +Average number of grid points per atom ... 1098 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24062 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2406 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.8636163679099553 0.00e+00 4.94e-04 3.80e-03 6.64e-03 0.700 0.1 + 2 -116.8638852374718198 -2.69e-04 4.88e-04 3.66e-03 5.26e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -116.8641029953666219 -2.18e-04 4.26e-04 3.08e-03 3.94e-03 0.700 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 4 -116.8642656521402756 -1.63e-04 1.10e-03 7.73e-03 2.84e-03 0.1 + *** Restarting incremental Fock matrix formation *** + 5 -116.8646788310493463 -4.13e-04 9.69e-05 6.40e-04 4.23e-04 0.1 + 6 -116.8646802528935069 -1.42e-06 5.94e-05 3.48e-04 9.63e-05 0.1 + 7 -116.8646803329201163 -8.00e-08 2.01e-05 1.06e-04 8.57e-05 0.1 + 8 -116.8646804139471698 -8.10e-08 4.78e-06 4.12e-05 1.81e-05 0.1 + 9 -116.8646804164237523 -2.48e-09 1.96e-06 1.28e-05 4.15e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.095 sec) +Old exchange energy : -3.604515937 Eh +New exchange energy : -3.604531140 Eh +Exchange energy change after final integration : -0.000015203 Eh +Total energy after final integration : -116.864695620 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86469561976341 Eh -3180.05004 eV + +Components: +Nuclear Repulsion : 74.85314429052390 Eh 2036.85761 eV +Electronic Energy : -191.71782470694765 Eh -5216.90723 eV +One Electron Energy: -304.74554775707696 Eh -8292.54794 eV +Two Electron Energy: 113.02772305012931 Eh 3075.64071 eV + +Virial components: +Potential Energy : -232.18013167295823 Eh -6317.94258 eV +Kinetic Energy : 115.31543605319480 Eh 3137.89254 eV +Virial Ratio : 2.01343497123710 + +DFT components: +N(Alpha) : 12.999999041649 electrons +N(Beta) : 11.999997329829 electrons +N(Total) : 24.999996371478 electrons +E(X) : -14.252579048574 Eh +E(C) : -0.919840286166 Eh +E(XC) : -15.172419334740 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.4766e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.2768e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 1.9595e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.8354e-03 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 4.1475e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 1.4922e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762376 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012376 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.4 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864695619763 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000644938 -0.000219545 -0.000008373 + 2 C : 0.000120046 0.000196962 0.000138159 + 3 C : -0.000337191 -0.000368194 -0.000015794 + 4 H : -0.000456002 0.000051519 0.000046795 + 5 H : -0.000225238 0.000040151 -0.000074762 + 6 H : 0.000090911 0.000012834 -0.000057713 + 7 H : 0.000060997 0.000076848 0.000218300 + 8 H : 0.000134466 0.000262795 0.000164888 + 9 H : -0.000053065 0.000003816 -0.000387445 + 10 H : 0.000020139 -0.000057187 -0.000024055 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000164690 0.0000129476 -0.0000554276 + +Norm of the Cartesian gradient ... 0.0011820780 +RMS gradient ... 0.0002158169 +MAX gradient ... 0.0006449385 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.654 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.117 sec ( 17.9%) +COSX gradient .... 0.412 sec ( 63.0%) +XC gradient .... 0.119 sec ( 18.3%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864695620 Eh +Current gradient norm .... 0.001182078 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.338 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124734025 0.001568005 0.027981166 0.042238302 0.052638958 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473403 and components: + 1. 0.00328079 + 2. 0.04861525 + 3. 0.55530766 + 4. -0.51888915 + 5. -0.01021985 + 6. -0.01338632 + 7. -0.00012109 + 8. -0.00673834 + 9. 0.00154451 + 10. -0.00817036 + 11. -0.29872700 + 12. 0.01844153 + 13. 0.00379967 + 14. -0.00958117 + 15. 0.07008541 + 16. 0.01713678 + 17. 0.31183772 + 18. 0.03259241 + 19. -0.04636367 + 20. 0.03140104 + 21. -0.06041735 + 22. -0.09278114 + 23. 0.00529852 + 24. -0.02163497 + 25. 0.00854935 + 26. 0.01349336 + 27. 0.00217890 + 28. -0.00775753 + 29. -0.01311071 + 30. -0.10057655 + 31. 0.15593331 + 32. -0.14344188 + 33. -0.06154766 + 34. 0.11690442 + 35. 0.03902889 + 36. -0.16495502 + 37. 0.01044895 + 38. 0.17085294 + 39. -0.15695855 + 40. 0.00245248 + 41. 0.16285647 + 42. -0.10851065 + 43. 0.09028481 + 44. -0.06773314 + 45. 0.06217307 + +Lambda that maximizes along the TS mode: 0.00000039 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00020042 step = 0.00020042 +In cycle 2: lambdaN = -0.00020337 step = 0.00000295 +In cycle 3: lambdaN = -0.00020337 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00020337 +The final length of the internal step .... 0.3367 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0501943092 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0688061821 RMS(Int)= 0.0500543001 + Iter 5: RMS(Cart)= 0.0000001506 RMS(Int)= 0.0000001171 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000113018 +Previously predicted energy change .... -0.000182210 +Actually observed energy change .... -0.000176785 +Ratio of predicted to observed change .... 0.970228242 +New trust radius .... 0.506250000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001767850 0.0000050000 NO + RMS gradient 0.0001301533 0.0001000000 NO + MAX gradient 0.0002932923 0.0003000000 YES + RMS step 0.0501943092 0.0020000000 NO + MAX step 0.1430011722 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0015 Max(Angles) 0.80 + Max(Dihed) 8.19 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5279 -0.000262 0.0009 1.5288 + 2. B(C 2,C 1) 1.5292 -0.000126 -0.0006 1.5286 + 3. B(H 3,C 0) 1.3317 -0.000064 -0.0015 1.3302 0.56 + 4. B(H 3,C 1) 1.3178 0.000189 0.0005 1.3182 0.52 + 5. B(H 4,C 0) 1.0929 -0.000045 0.0000 1.0929 + 6. B(H 5,C 0) 1.0933 -0.000039 -0.0000 1.0932 + 7. B(H 6,C 1) 1.0968 -0.000065 0.0001 1.0970 + 8. B(H 7,C 2) 1.1023 -0.000027 -0.0003 1.1019 + 9. B(H 8,C 2) 1.1020 -0.000067 0.0005 1.1025 + 10. B(H 9,C 2) 1.1061 0.000054 0.0001 1.1062 + 11. A(C 1,C 0,H 3) 54.36 0.000152 0.02 54.38 0.30 + 12. A(C 1,C 0,H 5) 118.77 -0.000134 -0.15 118.62 + 13. A(H 3,C 0,H 4) 114.55 0.000126 0.39 114.94 + 14. A(C 1,C 0,H 4) 118.56 0.000171 0.10 118.66 + 15. A(H 4,C 0,H 5) 118.43 -0.000072 0.04 118.46 + 16. A(H 3,C 0,H 5) 115.71 -0.000121 -0.42 115.29 + 17. A(C 0,C 1,H 3) 55.21 0.000011 -0.10 55.11 0.31 + 18. A(H 3,C 1,H 6) 111.81 -0.000037 0.55 112.36 + 19. A(C 2,C 1,H 6) 118.19 -0.000019 0.05 118.24 + 20. A(C 0,C 1,H 6) 115.86 -0.000003 0.26 116.11 + 21. A(C 0,C 1,C 2) 120.80 -0.000027 -0.09 120.71 + 22. A(C 2,C 1,H 3) 119.33 0.000110 -0.80 118.52 + 23. A(C 1,C 2,H 8) 111.01 -0.000080 0.29 111.30 + 24. A(C 1,C 2,H 7) 110.93 -0.000019 -0.29 110.63 + 25. A(H 7,C 2,H 9) 107.49 -0.000024 0.01 107.50 + 26. A(C 1,C 2,H 9) 111.35 0.000057 -0.04 111.31 + 27. A(H 7,C 2,H 8) 108.16 0.000051 0.09 108.25 + 28. A(H 8,C 2,H 9) 107.74 0.000017 -0.06 107.68 + 29. A(C 0,H 3,C 1) 70.43 -0.000163 0.08 70.51 + 30. D(H 3,C 1,C 0,H 5) 102.43 -0.000012 -0.44 101.99 + 31. D(C 2,C 1,C 0,H 4) 5.22 0.000040 -1.48 3.73 + 32. D(H 6,C 1,C 0,H 3) -99.56 0.000042 -0.50 -100.06 + 33. D(C 2,C 1,C 0,H 5) -151.30 0.000148 -1.46 -152.76 + 34. D(H 3,C 1,C 0,H 4) -101.05 -0.000120 -0.46 -101.51 + 35. D(C 2,C 1,C 0,H 3) 106.27 0.000160 -1.02 105.25 + 36. D(H 7,C 2,C 1,C 0) -44.30 -0.000293 8.19 -36.10 + 37. D(H 8,C 2,C 1,H 6) 41.83 -0.000175 7.50 49.33 + 38. D(H 8,C 2,C 1,H 3) -99.86 -0.000245 7.62 -92.24 + 39. D(H 8,C 2,C 1,C 0) -164.58 -0.000292 8.08 -156.50 + 40. D(H 7,C 2,C 1,H 6) 162.12 -0.000176 7.61 169.73 + 41. D(H 7,C 2,C 1,H 3) 20.43 -0.000246 7.73 28.16 + 42. D(C 0,H 3,C 1,C 2) -108.96 0.000089 -0.29 -109.25 + 43. D(C 1,H 3,C 0,H 5) -108.18 0.000056 -0.07 -108.25 + 44. D(C 1,H 3,C 0,H 4) 108.62 0.000175 -0.10 108.51 + 45. D(C 0,H 3,C 1,H 6) 107.09 0.000021 -0.04 107.06 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (18.595 %) +Internal coordinates : 0.000 s ( 1.476 %) +B/P matrices and projection : 0.000 s (13.577 %) +Hessian update/contruction : 0.000 s (12.869 %) +Making the step : 0.001 s (17.237 %) +Converting the step to Cartesian: 0.000 s ( 2.538 %) +Storing new data : 0.000 s ( 1.387 %) +Checking convergence : 0.000 s ( 0.561 %) +Final printing : 0.001 s (31.641 %) +Total time : 0.003 s + +Time for energy+gradient : 5.558 s +Time for complete geometry iter : 6.394 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 12 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.405546 -0.056471 0.105304 + C -0.024992 0.537765 -0.174267 + C 1.235150 -0.316425 -0.036280 + H -0.744554 0.777012 0.904013 + H -1.469877 -1.086326 0.465543 + H -2.273096 0.372988 -0.402707 + H 0.002000 1.396038 -0.856866 + H 1.135543 -1.022578 0.803769 + H 2.125426 0.309021 0.142065 + H 1.419946 -0.911025 -0.950574 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.656097 -0.106714 0.198996 + 1 C 6.0000 0 12.011 -0.047228 1.016228 -0.329316 + 2 C 6.0000 0 12.011 2.334095 -0.597956 -0.068559 + 3 H 1.0000 0 1.008 -1.407003 1.468341 1.708337 + 4 H 1.0000 0 1.008 -2.777665 -2.052858 0.879748 + 5 H 1.0000 0 1.008 -4.295529 0.704846 -0.761006 + 6 H 1.0000 0 1.008 0.003779 2.638130 -1.619242 + 7 H 1.0000 0 1.008 2.145865 -1.932393 1.518903 + 8 H 1.0000 0 1.008 4.016473 0.583964 0.268464 + 9 H 1.0000 0 1.008 2.683309 -1.721588 -1.796325 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.528791711600 0.00000000 0.00000000 + C 2 1 0 1.528606417563 120.71222814 0.00000000 + H 2 1 3 1.318216913720 55.11225325 254.75372651 + H 1 2 3 1.092937342113 118.66513706 3.73397160 + H 1 2 3 1.093230806428 118.61666186 207.23540368 + H 2 1 3 1.096952167733 116.11262439 154.69149621 + H 3 2 1 1.101932550943 110.63402398 323.90040910 + H 3 2 1 1.102533542941 111.30118046 203.50020271 + H 3 2 1 1.106179511566 111.31394876 83.36352949 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.888997650734 0.00000000 0.00000000 + C 2 1 0 2.888647495749 120.71222814 0.00000000 + H 2 1 3 2.491068952033 55.11225325 254.75372651 + H 1 2 3 2.065352258129 118.66513706 3.73397160 + H 1 2 3 2.065906825315 118.61666186 207.23540368 + H 2 1 3 2.072939179027 116.11262439 154.69149621 + H 3 2 1 2.082350739335 110.63402398 323.90040910 + H 3 2 1 2.083486449621 111.30118046 203.50020271 + H 3 2 1 2.090376331814 111.31394876 83.36352949 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.863991663677 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.241e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40944 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4094 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5296 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10970 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24053 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2405 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.3 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + 1 -116.8624184157735186 0.00e+00 7.41e-04 5.63e-03 9.85e-03 0.700 0.1 + 2 -116.8630223507089028 -6.04e-04 7.32e-04 5.42e-03 7.80e-03 0.700 0.1 + ***Turning on AO-DIIS*** + 3 -116.8635113913936863 -4.89e-04 6.38e-04 4.57e-03 5.84e-03 0.700 0.1 + 4 -116.8638766271188132 -3.65e-04 1.65e-03 1.14e-02 4.20e-03 0.000 0.1 + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 5 -116.8648043741209648 -9.28e-04 9.70e-05 5.92e-04 3.27e-04 0.1 + *** Restarting incremental Fock matrix formation *** + 6 -116.8648061952919335 -1.82e-06 7.53e-05 5.05e-04 3.36e-04 0.1 + 7 -116.8648070589607499 -8.64e-07 3.70e-05 2.99e-04 1.18e-04 0.1 + 8 -116.8648071601511305 -1.01e-07 1.18e-05 8.38e-05 3.43e-05 0.1 + 9 -116.8648071622642846 -2.11e-09 4.42e-06 2.36e-05 2.01e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 9 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.604517477 Eh +New exchange energy : -3.604505980 Eh +Exchange energy change after final integration : 0.000011497 Eh +Total energy after final integration : -116.864795665 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86479566493024 Eh -3180.05276 eV + +Components: +Nuclear Repulsion : 74.86399166367671 Eh 2037.15278 eV +Electronic Energy : -191.72879882594100 Eh -5217.20585 eV +One Electron Energy: -304.76626226027730 Eh -8293.11161 eV +Two Electron Energy: 113.03746343433630 Eh 3075.90576 eV + +Virial components: +Potential Energy : -232.17964427904275 Eh -6317.92932 eV +Kinetic Energy : 115.31484861411252 Eh 3137.87656 eV +Virial Ratio : 2.01344100147939 + +DFT components: +N(Alpha) : 13.000002796108 electrons +N(Beta) : 12.000000170729 electrons +N(Total) : 25.000002966836 electrons +E(X) : -14.252484551180 Eh +E(C) : -0.919863854256 Eh +E(XC) : -15.172348405436 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 2.1132e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.3629e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 4.4183e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 3.2722e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 2.0142e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.2595e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762330 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012330 + +Total SCF time: 0 days 0 hours 0 min 1 sec +Finished LeanSCF after 1.2 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.5 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864795664930 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.5 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000502629 -0.000733048 0.000299003 + 2 C : -0.000022543 0.000645038 0.000015254 + 3 C : -0.000127966 -0.000001046 0.000104208 + 4 H : -0.000032850 0.000053226 -0.000073383 + 5 H : -0.000273553 -0.000012661 -0.000137235 + 6 H : 0.000059841 0.000162821 0.000053020 + 7 H : 0.000111977 -0.000074485 -0.000106505 + 8 H : -0.000225167 0.000029161 -0.000010214 + 9 H : -0.000042528 0.000022060 -0.000090973 + 10 H : 0.000050160 -0.000091067 -0.000053175 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000222577 -0.0000255714 -0.0000932567 + +Norm of the Cartesian gradient ... 0.0012509063 +RMS gradient ... 0.0002283832 +MAX gradient ... 0.0007330481 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.722 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.7%) +RI-J Coulomb gradient .... 0.117 sec ( 16.2%) +COSX gradient .... 0.465 sec ( 64.4%) +XC gradient .... 0.135 sec ( 18.7%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864795665 Eh +Current gradient norm .... 0.001250906 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.506 +Updating the Hessian (Bofill) .... done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124736676 0.001815472 0.027976081 0.042246652 0.052638990 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473668 and components: + 1. -0.00327493 + 2. -0.04861022 + 3. -0.55531618 + 4. 0.51889159 + 5. 0.01022041 + 6. 0.01338601 + 7. 0.00012122 + 8. 0.00673498 + 9. -0.00153858 + 10. 0.00816702 + 11. 0.29872778 + 12. -0.01844841 + 13. -0.00377550 + 14. 0.00957920 + 15. -0.07007833 + 16. -0.01716336 + 17. -0.31184311 + 18. -0.03255562 + 19. 0.04636109 + 20. -0.03138781 + 21. 0.06042784 + 22. 0.09271854 + 23. -0.00527417 + 24. 0.02162475 + 25. -0.00854813 + 26. -0.01350205 + 27. -0.00217937 + 28. 0.00775067 + 29. 0.01311532 + 30. 0.10054694 + 31. -0.15605596 + 32. 0.14340488 + 33. 0.06142825 + 34. -0.11693726 + 35. -0.03911869 + 36. 0.16568149 + 37. -0.00978828 + 38. -0.17016306 + 39. 0.15767676 + 40. -0.00178355 + 41. -0.16215833 + 42. 0.10846308 + 43. -0.09029220 + 44. 0.06771656 + 45. -0.06218013 + +Lambda that maximizes along the TS mode: 0.00000004 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00000436 step = 0.00000436 +In cycle 2: lambdaN = -0.00000436 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00000436 +The final length of the internal step .... 0.0085 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0012731470 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0017935545 RMS(Int)= 0.0012727038 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000002157 +Previously predicted energy change .... -0.000113018 +Actually observed energy change .... -0.000100045 +Ratio of predicted to observed change .... 0.885218320 +New trust radius .... 0.700000000 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0001000452 0.0000050000 NO + RMS gradient 0.0001310768 0.0001000000 NO + MAX gradient 0.0003463796 0.0003000000 NO + RMS step 0.0012731470 0.0020000000 YES + MAX step 0.0042226659 0.0040000000 NO + ........................................................ + Max(Bonds) 0.0004 Max(Angles) 0.11 + Max(Dihed) 0.24 Max(Improp) 0.00 + --------------------------------------------------------------------- + +The optimization has not yet converged - more geometry cycles are needed + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + (Angstroem and degrees) + + Definition Value dE/dq Step New-Value comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5288 -0.000035 -0.0000 1.5288 + 2. B(C 2,C 1) 1.5286 -0.000270 0.0004 1.5290 + 3. B(H 3,C 0) 1.3302 0.000078 0.0002 1.3304 0.56 + 4. B(H 3,C 1) 1.3182 -0.000060 -0.0001 1.3182 0.52 + 5. B(H 4,C 0) 1.0929 -0.000014 0.0000 1.0930 + 6. B(H 5,C 0) 1.0932 -0.000010 0.0000 1.0932 + 7. B(H 6,C 1) 1.0970 0.000010 -0.0000 1.0969 + 8. B(H 7,C 2) 1.1019 -0.000008 0.0000 1.1020 + 9. B(H 8,C 2) 1.1025 -0.000035 0.0000 1.1026 + 10. B(H 9,C 2) 1.1062 0.000101 -0.0002 1.1060 + 11. A(C 1,C 0,H 3) 54.38 -0.000028 -0.01 54.37 0.30 + 12. A(C 1,C 0,H 5) 118.62 -0.000141 0.03 118.64 + 13. A(H 3,C 0,H 4) 114.94 0.000191 -0.08 114.87 + 14. A(C 1,C 0,H 4) 118.67 0.000228 -0.06 118.61 + 15. A(H 4,C 0,H 5) 118.46 -0.000075 0.02 118.48 + 16. A(H 3,C 0,H 5) 115.29 -0.000144 0.09 115.38 + 17. A(C 0,C 1,H 3) 55.11 0.000050 0.01 55.12 0.31 + 18. A(H 3,C 1,H 6) 112.36 0.000135 -0.10 112.26 + 19. A(C 2,C 1,H 6) 118.24 0.000080 -0.03 118.21 + 20. A(C 0,C 1,H 6) 116.11 0.000160 -0.02 116.09 + 21. A(C 0,C 1,C 2) 120.71 -0.000295 0.11 120.82 + 22. A(C 2,C 1,H 3) 118.53 -0.000132 0.03 118.55 + 23. A(C 1,C 2,H 8) 111.30 0.000015 -0.01 111.29 + 24. A(C 1,C 2,H 7) 110.63 -0.000346 0.07 110.70 + 25. A(H 7,C 2,H 9) 107.50 -0.000006 0.00 107.51 + 26. A(C 1,C 2,H 9) 111.31 0.000127 -0.02 111.29 + 27. A(H 7,C 2,H 8) 108.25 0.000187 -0.04 108.21 + 28. A(H 8,C 2,H 9) 107.68 0.000035 -0.00 107.68 + 29. A(C 0,H 3,C 1) 70.51 -0.000022 -0.00 70.51 + 30. D(H 3,C 1,C 0,H 5) 101.99 -0.000111 0.10 102.08 + 31. D(C 2,C 1,C 0,H 4) 3.73 -0.000079 0.05 3.78 + 32. D(H 6,C 1,C 0,H 3) -100.06 -0.000092 0.11 -99.96 + 33. D(C 2,C 1,C 0,H 5) -152.76 -0.000095 0.08 -152.69 + 34. D(H 3,C 1,C 0,H 4) -101.51 -0.000094 0.07 -101.44 + 35. D(C 2,C 1,C 0,H 3) 105.25 0.000016 -0.02 105.23 + 36. D(H 7,C 2,C 1,C 0) -36.10 -0.000005 -0.11 -36.21 + 37. D(H 8,C 2,C 1,H 6) 49.33 0.000076 -0.23 49.10 + 38. D(H 8,C 2,C 1,H 3) -92.24 -0.000103 -0.03 -92.27 + 39. D(H 8,C 2,C 1,C 0) -156.50 -0.000018 -0.10 -156.60 + 40. D(H 7,C 2,C 1,H 6) 169.73 0.000088 -0.24 169.49 + 41. D(H 7,C 2,C 1,H 3) 28.16 -0.000091 -0.05 28.11 + 42. D(C 0,H 3,C 1,C 2) -109.25 0.000284 -0.13 -109.38 + 43. D(C 1,H 3,C 0,H 5) -108.25 0.000098 0.02 -108.23 + 44. D(C 1,H 3,C 0,H 4) 108.51 0.000165 -0.02 108.49 + 45. D(C 0,H 3,C 1,H 6) 107.06 0.000127 0.03 107.09 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s (18.921 %) +Internal coordinates : 0.000 s ( 1.545 %) +B/P matrices and projection : 0.000 s (13.655 %) +Hessian update/contruction : 0.000 s (12.204 %) +Making the step : 0.001 s (17.471 %) +Converting the step to Cartesian: 0.000 s ( 1.798 %) +Storing new data : 0.000 s ( 1.451 %) +Checking convergence : 0.000 s ( 0.788 %) +Final printing : 0.001 s (32.040 %) +Total time : 0.003 s + +Time for energy+gradient : 5.749 s +Time for complete geometry iter : 6.631 s + + ************************************************************* + * GEOMETRY OPTIMIZATION CYCLE 13 * + ************************************************************* +--------------------------------- +CARTESIAN COORDINATES (ANGSTROEM) +--------------------------------- + C -1.406738 -0.055989 0.104836 + C -0.025422 0.536744 -0.174024 + C 1.235706 -0.316773 -0.036294 + H -0.744855 0.776523 0.904136 + H -1.471251 -1.085631 0.465702 + H -2.273752 0.373300 -0.404253 + H 0.002125 1.396369 -0.854873 + H 1.138606 -1.022325 0.804576 + H 2.125738 0.309548 0.140469 + H 1.419843 -0.911766 -0.950274 + +---------------------------- +CARTESIAN COORDINATES (A.U.) +---------------------------- + NO LB ZA FRAG MASS X Y Z + 0 C 6.0000 0 12.011 -2.658349 -0.105804 0.198111 + 1 C 6.0000 0 12.011 -0.048040 1.014300 -0.328858 + 2 C 6.0000 0 12.011 2.335145 -0.598615 -0.068586 + 3 H 1.0000 0 1.008 -1.407571 1.467416 1.708569 + 4 H 1.0000 0 1.008 -2.780262 -2.051545 0.880050 + 5 H 1.0000 0 1.008 -4.296769 0.705435 -0.763928 + 6 H 1.0000 0 1.008 0.004016 2.638756 -1.615477 + 7 H 1.0000 0 1.008 2.151653 -1.931915 1.520428 + 8 H 1.0000 0 1.008 4.017062 0.584961 0.265448 + 9 H 1.0000 0 1.008 2.683115 -1.722989 -1.795758 + +-------------------------------- +INTERNAL COORDINATES (ANGSTROEM) +-------------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 1.528767063306 0.00000000 0.00000000 + C 2 1 0 1.529020585899 120.82257540 0.00000000 + H 2 1 3 1.318144711797 55.12280079 254.77242959 + H 1 2 3 1.092954083674 118.60840761 3.78442511 + H 1 2 3 1.093240758917 118.64530089 207.31221698 + H 2 1 3 1.096936750005 116.08784844 154.81727650 + H 3 2 1 1.101950363160 110.69953059 323.78995607 + H 3 2 1 1.102578980823 111.29344030 203.40423204 + H 3 2 1 1.106021211482 111.29530582 83.28952957 + +--------------------------- +INTERNAL COORDINATES (A.U.) +--------------------------- + C 0 0 0 0.000000000000 0.00000000 0.00000000 + C 1 0 0 2.888951072208 0.00000000 0.00000000 + C 2 1 0 2.889430160478 120.82257540 0.00000000 + H 2 1 3 2.490932510172 55.12280079 254.77242959 + H 1 2 3 2.065383895096 118.60840761 3.78442511 + H 1 2 3 2.065925632793 118.64530089 207.31221698 + H 2 1 3 2.072910043743 116.08784844 154.81727650 + H 3 2 1 2.082384399547 110.69953059 323.78995607 + H 3 2 1 2.083572314773 111.29344030 203.40423204 + H 3 2 1 2.090077188009 111.29530582 83.28952957 + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.850974442568 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.242e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40946 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5297 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10971 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24053 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2405 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8648082297359565 0.00e+00 7.15e-05 3.96e-04 9.93e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8648095911690064 -1.36e-06 4.00e-05 2.55e-04 1.33e-04 0.1 + 3 -116.8648097928207221 -2.02e-07 9.28e-06 5.55e-05 2.46e-05 0.1 + 4 -116.8648097997800051 -6.96e-09 2.06e-06 1.36e-05 7.29e-06 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.098 sec) +Old exchange energy : -3.604484600 Eh +New exchange energy : -3.604473812 Eh +Exchange energy change after final integration : 0.000010788 Eh +Total energy after final integration : -116.864799012 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86479901191194 Eh -3180.05285 eV + +Components: +Nuclear Repulsion : 74.85097444256775 Eh 2036.79856 eV +Electronic Energy : -191.71578424234775 Eh -5216.85171 eV +One Electron Energy: -304.74032021311109 Eh -8292.40569 eV +Two Electron Energy: 113.02453597076334 Eh 3075.55398 eV + +Virial components: +Potential Energy : -232.17909203334506 Eh -6317.91429 eV +Kinetic Energy : 115.31429302143312 Eh 3137.86144 eV +Virial Ratio : 2.01344591333696 + +DFT components: +N(Alpha) : 13.000002908638 electrons +N(Beta) : 12.000000329614 electrons +N(Total) : 25.000003238251 electrons +E(X) : -14.252377654558 Eh +E(C) : -0.919847766759 Eh +E(XC) : -15.172225421317 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 6.9593e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 1.3590e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 2.0645e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 1.9864e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 7.2911e-06 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.5899e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762333 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012333 + +Total SCF time: 0 days 0 hours 0 min 0 sec +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.6 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864799011912 +------------------------- -------------------- + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA SCF GRADIENT CALCULATION +------------------------------------------------------------------------------ + +Nuc. rep. gradient (SHARK) ... done ( 0.0 sec) +HCore & Overlap gradient (SHARK) ... done ( 0.0 sec) +Split-RIJ-J gradient (SHARK) ... done ( 0.1 sec) +COSX-gradient ... done ( 0.4 sec) +XC gradient ... done ( 0.1 sec) + +------------------ +CARTESIAN GRADIENT +------------------ + + 1 C : 0.000373304 -0.000486422 0.000248671 + 2 C : -0.000209842 0.000504978 -0.000157858 + 3 C : 0.000029114 -0.000118061 0.000060364 + 4 H : -0.000074219 0.000019004 -0.000020566 + 5 H : -0.000198710 -0.000019193 -0.000113179 + 6 H : 0.000037524 0.000146811 0.000049142 + 7 H : 0.000093949 -0.000050920 -0.000059432 + 8 H : -0.000087537 0.000025451 0.000008599 + 9 H : 0.000021300 -0.000014651 -0.000049797 + 10 H : 0.000015117 -0.000006997 0.000034056 + +Difference to translation invariance: + : 0.0000000000 0.0000000000 -0.0000000000 + +Difference to rotation invariance: + : -0.0000258523 -0.0000252937 -0.0000930258 + +Norm of the Cartesian gradient ... 0.0009446896 +RMS gradient ... 0.0001724759 +MAX gradient ... 0.0005049779 + +------- +TIMINGS +------- + +Total SCF gradient time .... 0.660 sec + +Densities .... 0.000 sec ( 0.0%) +One electron gradient .... 0.005 sec ( 0.8%) +RI-J Coulomb gradient .... 0.115 sec ( 17.4%) +COSX gradient .... 0.420 sec ( 63.6%) +XC gradient .... 0.120 sec ( 18.2%) + +Maximum memory used throughout the entire SCFGRAD-calculation: 7.8 MB +------------------------------------------------------------------------------ + ORCA GEOMETRY RELAXATION STEP +------------------------------------------------------------------------------ + +Reading the OPT-File .... done +Getting information on internals .... done +Copying old internal coords+grads .... done +Making the new internal coordinates .... (2022 redundants) done +Validating the new internal coordinates .... (2022 redundants) done +Calculating the B-matrix .... done +Calculating the G,G- and P matrices .... done +Transforming gradient to internals .... done +Projecting the internal gradient .... done +Number of atoms .... 10 +Number of internal coordinates .... 45 +Current Energy .... -116.864799012 Eh +Current gradient norm .... 0.000944690 Eh/bohr +Maximum allowed component of the step .... 0.300 +Current trust radius .... 0.700 + +(DQ * DQ)^2 = 0.00000000930307 Bofill update is skipped +Updating the Hessian (Bofill) .... +(DQ * DQ)^2 = 0.00000000531362 Bofill update is skipped +done +Diagonalizing the Hessian .... done +Dimension of the hessian .... 45 +Lowest eigenvalues of the Hessian: + -0.124736676 0.001815472 0.027976081 0.042246652 0.052638990 +Hessian has 1 negative eigenvalues +Taking P-RFO step +Searching for lambda that maximizes along the lowest mode +TS mode is mode number 0 with eigenvalue -0.12473668 and components: + 1. -0.00327493 + 2. -0.04861022 + 3. -0.55531618 + 4. 0.51889159 + 5. 0.01022041 + 6. 0.01338601 + 7. 0.00012122 + 8. 0.00673498 + 9. -0.00153858 + 10. 0.00816702 + 11. 0.29872778 + 12. -0.01844841 + 13. -0.00377550 + 14. 0.00957920 + 15. -0.07007833 + 16. -0.01716336 + 17. -0.31184311 + 18. -0.03255562 + 19. 0.04636109 + 20. -0.03138781 + 21. 0.06042784 + 22. 0.09271854 + 23. -0.00527417 + 24. 0.02162475 + 25. -0.00854813 + 26. -0.01350205 + 27. -0.00217937 + 28. 0.00775067 + 29. 0.01311532 + 30. 0.10054694 + 31. -0.15605596 + 32. 0.14340488 + 33. 0.06142825 + 34. -0.11693726 + 35. -0.03911869 + 36. 0.16568149 + 37. -0.00978828 + 38. -0.17016306 + 39. 0.15767676 + 40. -0.00178355 + 41. -0.16215833 + 42. 0.10846308 + 43. -0.09029220 + 44. 0.06771656 + 45. -0.06218013 + +Lambda that maximizes along the TS mode: 0.00000000 +Searching for lambda that minimizes along all other modes +In cycle 1: lambdaN = -0.00000180 step = 0.00000180 +In cycle 2: lambdaN = -0.00000180 step = 0.00000000 +Lambda that minimizes along all other modes: -0.00000180 +The final length of the internal step .... 0.0060 +Converting the step to Cartesian space: + Initial RMS(Int)= 0.0008940734 +Transforming coordinates: + Iter 0: RMS(Cart)= 0.0013182464 RMS(Int)= 0.0008940011 +done +Storing new coordinates .... done +The predicted energy change is .... -0.000000901 +Previously predicted energy change .... -0.000002157 +Actually observed energy change .... -0.000003347 +Ratio of predicted to observed change .... 1.551427627 +New trust radius .... 0.466666667 + + .--------------------. + ----------------------|Geometry convergence|------------------------- + Item value Tolerance Converged + --------------------------------------------------------------------- + Energy change -0.0000033470 0.0000050000 YES + RMS gradient 0.0000775083 0.0001000000 YES + MAX gradient 0.0001651341 0.0003000000 YES + RMS step 0.0008940734 0.0020000000 YES + MAX step 0.0025562854 0.0040000000 YES + ........................................................ + Max(Bonds) 0.0001 Max(Angles) 0.07 + Max(Dihed) 0.15 Max(Improp) 0.00 + --------------------------------------------------------------------- + + ***********************HURRAY******************** + *** THE OPTIMIZATION HAS CONVERGED *** + ************************************************* + + + --------------------------------------------------------------------------- + Redundant Internal Coordinates + + --- Optimized Parameters --- + (Angstroem and degrees) + + Definition OldVal dE/dq Step FinalVal comp.(TS mode) + ---------------------------------------------------------------------------- + 1. B(C 1,C 0) 1.5288 -0.000019 -0.0000 1.5288 + 2. B(C 2,C 1) 1.5290 0.000047 -0.0001 1.5290 + 3. B(H 3,C 0) 1.3304 0.000026 -0.0000 1.3304 0.56 + 4. B(H 3,C 1) 1.3181 0.000005 0.0000 1.3182 0.52 + 5. B(H 4,C 0) 1.0930 -0.000005 0.0000 1.0930 + 6. B(H 5,C 0) 1.0932 0.000004 -0.0000 1.0932 + 7. B(H 6,C 1) 1.0969 -0.000001 0.0000 1.0969 + 8. B(H 7,C 2) 1.1020 -0.000004 0.0000 1.1020 + 9. B(H 8,C 2) 1.1026 0.000003 0.0000 1.1026 + 10. B(H 9,C 2) 1.1060 -0.000022 0.0000 1.1061 + 11. A(C 1,C 0,H 3) 54.37 0.000003 0.00 54.37 0.30 + 12. A(C 1,C 0,H 5) 118.65 -0.000111 0.01 118.66 + 13. A(H 3,C 0,H 4) 114.87 0.000137 -0.05 114.81 + 14. A(C 1,C 0,H 4) 118.61 0.000165 -0.04 118.57 + 15. A(H 4,C 0,H 5) 118.48 -0.000046 0.01 118.49 + 16. A(H 3,C 0,H 5) 115.38 -0.000120 0.07 115.45 + 17. A(C 0,C 1,H 3) 55.12 0.000015 -0.00 55.12 0.31 + 18. A(H 3,C 1,H 6) 112.26 0.000100 -0.06 112.21 + 19. A(C 2,C 1,H 6) 118.21 0.000029 -0.01 118.19 + 20. A(C 0,C 1,H 6) 116.09 0.000108 -0.01 116.07 + 21. A(C 0,C 1,C 2) 120.82 -0.000164 0.05 120.88 + 22. A(C 2,C 1,H 3) 118.56 -0.000084 0.03 118.59 + 23. A(C 1,C 2,H 8) 111.29 0.000069 -0.01 111.28 + 24. A(C 1,C 2,H 7) 110.70 -0.000162 0.03 110.73 + 25. A(H 7,C 2,H 9) 107.51 -0.000014 0.00 107.51 + 26. A(C 1,C 2,H 9) 111.30 0.000052 -0.01 111.29 + 27. A(H 7,C 2,H 8) 108.21 0.000056 -0.01 108.20 + 28. A(H 8,C 2,H 9) 107.68 0.000000 0.00 107.68 + 29. A(C 0,H 3,C 1) 70.51 -0.000018 -0.00 70.51 + 30. D(H 3,C 1,C 0,H 5) 102.08 -0.000086 0.08 102.17 + 31. D(C 2,C 1,C 0,H 4) 3.78 -0.000086 0.05 3.84 + 32. D(H 6,C 1,C 0,H 3) -99.96 -0.000066 0.06 -99.89 + 33. D(C 2,C 1,C 0,H 5) -152.69 -0.000096 0.09 -152.60 + 34. D(H 3,C 1,C 0,H 4) -101.44 -0.000076 0.04 -101.40 + 35. D(C 2,C 1,C 0,H 3) 105.23 -0.000010 0.01 105.24 + 36. D(H 7,C 2,C 1,C 0) -36.21 -0.000002 0.11 -36.10 + 37. D(H 8,C 2,C 1,H 6) 49.10 0.000030 0.06 49.16 + 38. D(H 8,C 2,C 1,H 3) -92.28 -0.000077 0.15 -92.13 + 39. D(H 8,C 2,C 1,C 0) -156.60 -0.000010 0.11 -156.48 + 40. D(H 7,C 2,C 1,H 6) 169.49 0.000037 0.05 169.54 + 41. D(H 7,C 2,C 1,H 3) 28.11 -0.000069 0.14 28.25 + 42. D(C 0,H 3,C 1,C 2) -109.37 0.000156 -0.05 -109.43 + 43. D(C 1,H 3,C 0,H 5) -108.23 0.000067 0.02 -108.20 + 44. D(C 1,H 3,C 0,H 4) 108.49 0.000126 -0.02 108.47 + 45. D(C 0,H 3,C 1,H 6) 107.09 0.000076 0.02 107.11 + ---------------------------------------------------------------------------- + +Geometry step timings: +Preparation and reading OPT file: 0.001 s ( 8.989 %) +Internal coordinates : 0.000 s ( 0.814 %) +B/P matrices and projection : 0.000 s ( 6.234 %) +Hessian update/contruction : 0.001 s ( 9.729 %) +Making the step : 0.001 s ( 8.707 %) +Converting the step to Cartesian: 0.000 s ( 1.111 %) +Storing new data : 0.000 s ( 0.874 %) +Checking convergence : 0.000 s ( 0.296 %) +Final printing : 0.004 s (63.202 %) +Total time : 0.007 s + ******************************************************* + *** FINAL ENERGY EVALUATION AT THE STATIONARY POINT *** + *** (AFTER 13 CYCLES) *** + ******************************************************* + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------ + ORCA STARTUP CALCULATIONS + -- RI-GTO INTEGRALS CHOSEN -- +------------------------------------------------------------------------------ +------------------------------------------------------------------------------ + ___ + / \ - P O W E R E D B Y - + / \ + | | | _ _ __ _____ __ __ + | | | | | | | / \ | _ \ | | / | + \ \/ | | | | / \ | | | | | | / / + / \ \ | |__| | / /\ \ | |_| | | |/ / + | | | | __ | / /__\ \ | / | \ + | | | | | | | | __ | | \ | |\ \ + \ / | | | | | | | | | |\ \ | | \ \ + \___/ |_| |_| |__| |__| |_| \__\ |__| \__/ + + - O R C A' S B I G F R I E N D - + & + - I N T E G R A L F E E D E R - + + v1 FN, 2020, v2 2021, v3 2022-2024 +------------------------------------------------------------------------------ + + +---------------------- +SHARK INTEGRAL PACKAGE +---------------------- + +Number of atoms ... 10 +Number of basis functions ... 22 +Number of shells ... 16 +Maximum angular momentum ... 1 +Integral batch strategy ... SHARK/LIBINT Hybrid +RI-J (if used) integral strategy ... SPLIT-RIJ (Revised 2003 algorithm where possible) +Printlevel ... 1 +Contraction scheme used ... SEGMENTED contraction +Prescreening option ... SCHWARTZ + Thresh ... 2.500e-11 + Tcut ... 2.500e-12 + Tpresel ... 2.500e-12 +Coulomb Range Separation ... NOT USED +Exchange Range Separation ... NOT USED +Multipole approximations ... NOT USED +Finite Nucleus Model ... NOT USED +CABS basis ... NOT available +Auxiliary Coulomb fitting basis ... AVAILABLE + # of basis functions in Aux-J ... 224 + # of shells in Aux-J ... 80 + Maximum angular momentum in Aux-J ... 4 +Auxiliary J/K fitting basis ... NOT available +Auxiliary Correlation fitting basis ... NOT available +Auxiliary 'external' fitting basis ... NOT available + +Checking pre-screening integrals ... done ( 0.0 sec) Dimension = 16 +Check shell pair data ... done ( 0.0 sec) +Shell pair information +Shell pair cut-off parameter TPreSel ... 2.5e-12 +Total number of shell pairs ... 136 +Shell pairs after pre-screening ... 135 +Total number of primitive shell pairs ... 1224 +Primitive shell pairs kept ... 1107 + la=0 lb=0: 90 shell pairs + la=1 lb=0: 39 shell pairs + la=1 lb=1: 6 shell pairs + +Calculating one electron integrals ... done ( 0.0 sec) +Calculating RI/J V-Matrix + Cholesky decomp.... done ( 0.0 sec) +Calculating Nuclear repulsion ... done ( 0.0 sec) ENN= 74.848803962032 Eh + +Diagonalization of the overlap matrix: +Smallest eigenvalue ... 2.242e-01 +Time for diagonalization ... 0.000 sec +Threshold for overlap eigenvalues ... 1.000e-07 +Number of eigenvalues below threshold ... 0 +Time for construction of square roots ... 0.000 sec +Total time needed ... 0.001 sec + +------------------- +DFT GRID GENERATION +------------------- + +General Integration Accuracy IntAcc ... 4.388 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 4 (Lebedev-302) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... off +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 40946 +Total number of batches ... 645 +Average number of points per batch ... 63 +Average number of grid points per atom ... 4095 + +-------------------- +COSX GRID GENERATION +-------------------- + +GRIDX 1 +------- +General Integration Accuracy IntAcc ... 3.816 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 1 (Lebedev-50) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 5297 +Total number of batches ... 48 +Average number of points per batch ... 110 +Average number of grid points per atom ... 530 +UseSFitting ... on + +GRIDX 2 +------- +General Integration Accuracy IntAcc ... 4.020 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 2 (Lebedev-110) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 10971 +Total number of batches ... 89 +Average number of points per batch ... 123 +Average number of grid points per atom ... 1097 +UseSFitting ... on + +GRIDX 3 +------- +General Integration Accuracy IntAcc ... 4.338 +Radial Grid Type RadialGrid ... OptM3 with GC (2021) +Angular Grid (max. ang.) AngularGrid ... 3 (Lebedev-194) +Angular grid pruning method GridPruning ... 4 (adaptive) +Weight generation scheme WeightScheme... mBecke (2022) +Basis function cutoff BFCut ... 1.0000e-11 +Integration weight cutoff WCut ... 1.0000e-14 +Partially contracted basis set ... on +Rotationally invariant grid construction ... off +Angular grids for H and He will be reduced by one unit + +Total number of grid points ... 24053 +Total number of batches ... 193 +Average number of points per batch ... 124 +Average number of grid points per atom ... 2405 +UseSFitting ... on +Initializing property integral containers ... done ( 0.0 sec) + +SHARK setup successfully completed in 0.4 seconds + +Maximum memory used throughout the entire STARTUP-calculation: 11.2 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ +------------------------------------------------------------------------------- + ORCA GUESS + Start orbitals & Density for SCF / CASSCF +------------------------------------------------------------------------------- + +------------ +SCF SETTINGS +------------ +Hamiltonian: + Density Functional Method .... DFT(GTOs) + Exchange Functional Exchange .... B88 + X-Alpha parameter XAlpha .... 0.666667 + Becke's b parameter XBeta .... 0.004200 + Correlation Functional Correlation .... LYP + LDA part of GGA corr. LDAOpt .... VWN-5 + Gradients option PostSCFGGA .... off + Hybrid DFT is turned on + Fraction HF Exchange ScalHFX .... 0.200000 + Scaling of DF-GGA-X ScalDFX .... 0.720000 + Scaling of DF-GGA-C ScalDFC .... 0.810000 + Scaling of DF-LDA-C ScalLDAC .... 1.000000 + Perturbative correction .... 0.000000 + NL short-range parameter .... 4.800000 + RI-approximation to the Coulomb term is turned on + Number of AuxJ basis functions .... 224 + RIJ-COSX (HFX calculated with COS-X)).... on + + +General Settings: + Integral files IntName .... input + Hartree-Fock type HFTyp .... UHF + Total Charge Charge .... 0 + Multiplicity Mult .... 2 + Number of Electrons NEL .... 25 + Basis Dimension Dim .... 22 + Nuclear Repulsion ENuc .... 74.8488039620 Eh + +Convergence Acceleration: + AO-DIIS CNVDIIS .... on + Start iteration DIISMaxIt .... 12 + Startup error DIISStart .... 0.200000 + # of expansion vecs DIISMaxEq .... 5 + Bias factor DIISBfac .... 1.050 + Max. coefficient DIISMaxC .... 10.000 + MO-DIIS CNVKDIIS .... off + Trust-Rad. Augm. Hess. CNVTRAH .... auto + Auto Start mean grad. ratio tolernc. .... 1.125000 + Auto Start start iteration .... 1 + Auto Start num. interpolation iter. .... 10 + Max. Number of Micro iterations .... 24 + Max. Number of Macro iterations .... Maxiter - #DIIS iter + Number of Davidson start vectors .... 2 + Converg. threshold (grad. norm) .... 1.000e-05 + Grad. Scal. Fac. for Micro threshold .... 0.100 + Minimum threshold for Micro iter. .... 1.000e-02 + NR start threshold (gradient norm) .... 1.000e-04 + Initial trust radius .... 0.400 + Minimum AH scaling param. (alpha) .... 1.000 + Maximum AH scaling param. (alpha) .... 1000.000 + Quad. conv. algorithm .... NR + White noise on init. David. guess .... on + Maximum white noise .... 0.010 + Pseudo random numbers .... off + Inactive MOs .... canonical + Orbital update algorithm .... Taylor + Preconditioner .... Diag + Full preconditioner red. dimension .... 250 + SOSCF CNVSOSCF .... on + Start iteration SOSCFMaxIt .... 150 + Startup grad/error SOSCFStart .... 0.003300 + Hessian update SOSCFHessUp .... L-BFGS + Level Shifting CNVShift .... on + Level shift para. LevelShift .... 0.2500 + Turn off err/grad. ShiftErr .... 0.0010 + Zerner damping CNVZerner .... off + Static damping CNVDamp .... on + Fraction old density DampFac .... 0.7000 + Max. Damping (<1) DampMax .... 0.9800 + Min. Damping (>=0) DampMin .... 0.0000 + Turn off err/grad. DampErr .... 0.1000 + +SCF Procedure: + Maximum # iterations MaxIter .... 125 + SCF integral mode SCFMode .... Direct + Integral package .... SHARK and LIBINT hybrid scheme + Reset frequency DirectResetFreq .... 20 + Integral Threshold Thresh .... 2.500e-11 Eh + Primitive CutOff TCut .... 2.500e-12 Eh + +Convergence Tolerance: + Convergence Check Mode ConvCheckMode .... Total+1el-Energy + Convergence forced ConvForced .... 0 + Energy Change TolE .... 1.000e-08 Eh + 1-El. energy change .... 1.000e-05 Eh + Orbital Gradient TolG .... 1.000e-05 + Orbital Rotation angle TolX .... 1.000e-05 + DIIS Error TolErr .... 5.000e-07 + +--------------------- +INITIAL GUESS: MOREAD +--------------------- +Guess MOs are being read from file: input.gbw +Input Geometry matches current geometry (good) +Input basis set matches current basis set (good) +MOs were renormalized +MOs were reorthogonalized (Cholesky) + ------------------ + INITIAL GUESS DONE ( 0.0 sec) + ------------------ + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** +Finished Guess after 0.2 sec +Maximum memory used throughout the entire GUESS-calculation: 4.7 MB + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------------------- + ORCA LEAN-SCF + memory conserving SCF solver +------------------------------------------------------------------------------------------- + +----------------------------------------D-I-I-S-------------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP DIISErr Damp Time(sec) +------------------------------------------------------------------------------------------- + *** Starting incremental Fock matrix formation *** + *** Initializing SOSCF *** +---------------------------------------S-O-S-C-F-------------------------------------- +Iteration Energy (Eh) Delta-E RMSDP MaxDP MaxGrad Time(sec) +-------------------------------------------------------------------------------------- + 1 -116.8648105050574770 0.00e+00 5.65e-05 3.34e-04 4.75e-05 0.1 + *** Restarting incremental Fock matrix formation *** + 2 -116.8648114102230693 -9.05e-07 3.14e-05 1.97e-04 6.54e-05 0.1 + 3 -116.8648115540533752 -1.44e-07 8.18e-06 6.16e-05 1.77e-05 0.1 + 4 -116.8648115584346669 -4.38e-09 3.73e-06 2.84e-05 1.41e-05 0.1 + **** Energy Check signals convergence **** + + ***************************************************** + * SUCCESS * + * SCF CONVERGED AFTER 4 CYCLES * + ***************************************************** + +Recomputing exchange energy using gridx3 ... done ( 0.096 sec) +Old exchange energy : -3.604485193 Eh +New exchange energy : -3.604474239 Eh +Exchange energy change after final integration : 0.000010954 Eh +Total energy after final integration : -116.864800604 Eh + **** ENERGY FILE WAS UPDATED (input.en.tmp) **** + +---------------- +TOTAL SCF ENERGY +---------------- + +Total Energy : -116.86480060429696 Eh -3180.05290 eV + +Components: +Nuclear Repulsion : 74.84880396203161 Eh 2036.73950 eV +Electronic Energy : -191.71361552046625 Eh -5216.79269 eV +One Electron Energy: -304.73590080383633 Eh -8292.28543 eV +Two Electron Energy: 113.02228528337007 Eh 3075.49274 eV + +Virial components: +Potential Energy : -232.17907719828867 Eh -6317.91389 eV +Kinetic Energy : 115.31427659399171 Eh 3137.86099 eV +Virial Ratio : 2.01344607151953 + +DFT components: +N(Alpha) : 13.000003013972 electrons +N(Beta) : 12.000000449240 electrons +N(Total) : 25.000003463212 electrons +E(X) : -14.252381637855 Eh +E(C) : -0.919847679713 Eh +E(XC) : -15.172229317568 Eh + +--------------- +SCF CONVERGENCE +--------------- + + Last Energy change ... 4.3813e-09 Tolerance : 1.0000e-08 + Last MAX-Density change ... 2.8435e-05 Tolerance : 1.0000e-07 + Last RMS-Density change ... 3.7300e-06 Tolerance : 5.0000e-09 + Last DIIS Error ... 2.1388e-04 Tolerance : 5.0000e-07 + Last Orbital Gradient ... 1.4073e-05 Tolerance : 1.0000e-05 + Last Orbital Rotation ... 2.6248e-05 Tolerance : 1.0000e-05 + + +---------------------- +UHF SPIN CONTAMINATION +---------------------- + +Warning: in a DFT calculation there is little theoretical justification to + calculate as in Hartree-Fock theory. We will do it anyways + but you should keep in mind that the values have only limited relevance + +Expectation value of : 0.762333 +Ideal value S*(S+1) for S=0.5 : 0.750000 +Deviation : 0.012333 + +---------------- +ORBITAL ENERGIES +---------------- + SPIN UP ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.003664 -272.2135 + 1 1.0000 -9.979746 -271.5627 + 2 1.0000 -9.965627 -271.1785 + 3 1.0000 -0.742424 -20.2024 + 4 1.0000 -0.645332 -17.5604 + 5 1.0000 -0.521092 -14.1796 + 6 1.0000 -0.425923 -11.5900 + 7 1.0000 -0.389759 -10.6059 + 8 1.0000 -0.366555 -9.9745 + 9 1.0000 -0.342575 -9.3219 + 10 1.0000 -0.308609 -8.3977 + 11 1.0000 -0.253637 -6.9018 + 12 1.0000 -0.057839 -1.5739 + 13 0.0000 0.306273 8.3341 + 14 0.0000 0.372146 10.1266 + 15 0.0000 0.406049 11.0491 + 16 0.0000 0.418141 11.3782 + 17 0.0000 0.453719 12.3463 + 18 0.0000 0.468729 12.7548 + 19 0.0000 0.487108 13.2549 + 20 0.0000 0.534820 14.5532 + 21 0.0000 0.593271 16.1437 + + SPIN DOWN ORBITALS + NO OCC E(Eh) E(eV) + 0 1.0000 -10.004033 -272.2236 + 1 1.0000 -9.970429 -271.3092 + 2 1.0000 -9.955883 -270.9134 + 3 1.0000 -0.722634 -19.6639 + 4 1.0000 -0.635194 -17.2845 + 5 1.0000 -0.500980 -13.6324 + 6 1.0000 -0.414527 -11.2798 + 7 1.0000 -0.378869 -10.3095 + 8 1.0000 -0.361125 -9.8267 + 9 1.0000 -0.337515 -9.1843 + 10 1.0000 -0.302930 -8.2431 + 11 1.0000 -0.226137 -6.1535 + 12 0.0000 0.098292 2.6747 + 13 0.0000 0.329565 8.9679 + 14 0.0000 0.387902 10.5553 + 15 0.0000 0.421644 11.4735 + 16 0.0000 0.430098 11.7036 + 17 0.0000 0.463898 12.6233 + 18 0.0000 0.477826 13.0023 + 19 0.0000 0.490364 13.3435 + 20 0.0000 0.547393 14.8953 + 21 0.0000 0.607138 16.5211 +*Only the first 10 virtual orbitals were printed. +------- +TIMINGS +------- + +Total SCF time: 0 days 0 hours 0 min 0 sec + +Total time .... 0.809 sec +Sum of individual times .... 0.786 sec ( 97.2%) + +SCF preparation .... 0.250 sec ( 30.9%) +Fock matrix formation .... 0.489 sec ( 60.4%) + Startup .... 0.007 sec ( 1.3% of F) + Split-RI-J .... 0.026 sec ( 5.4% of F) + Chain of spheres X .... 0.308 sec ( 63.0% of F) + XC integration .... 0.130 sec ( 26.6% of F) + Basis function eval. .... 0.032 sec ( 24.6% of XC) + Density eval. .... 0.010 sec ( 7.5% of XC) + XC-Functional eval. .... 0.029 sec ( 22.3% of XC) + XC-Potential eval. .... 0.008 sec ( 5.8% of XC) +Diagonalization .... 0.000 sec ( 0.0%) +Density matrix formation .... 0.006 sec ( 0.8%) +Total Energy calculation .... 0.007 sec ( 0.9%) +Population analysis .... 0.000 sec ( 0.0%) +Orbital Transformation .... 0.006 sec ( 0.7%) +Orbital Orthonormalization .... 0.000 sec ( 0.0%) +DIIS solution .... 0.008 sec ( 0.9%) +SOSCF solution .... 0.020 sec ( 2.5%) +Finished LeanSCF after 0.8 sec + +Maximum memory used throughout the entire LEANSCF-calculation: 7.6 MB + +------------------------- -------------------- +FINAL SINGLE POINT ENERGY -116.864800604297 +------------------------- -------------------- + + *** OPTIMIZATION RUN DONE *** + + + + ***********************HURRAY************************ + *** THE TS OPTIMIZATION HAS CONVERGED *** + ***************************************************** + + + +--------------------------------------------------------------- + PATH SUMMARY FOR NEB-TS +--------------------------------------------------------------- +All forces in Eh/Bohr. Global forces for TS. + +Image E(Eh) dE(kcal/mol) max(|Fp|) RMS(Fp) + 0 -116.96634 0.00 0.00010 0.00004 + 1 -116.96621 0.08 0.00051 0.00021 + 2 -116.96401 1.47 0.00286 0.00142 + 3 -116.93955 16.81 0.00748 0.00372 + 4 -116.90788 36.69 0.01748 0.00613 + 5 -116.87566 56.90 0.00912 0.00342 + 6 -116.86298 64.86 0.00139 0.00072 <= CI + TS -116.86480 63.72 0.00050 0.00017 <= TS + 7 -116.88248 52.62 0.01092 0.00315 + 8 -116.91937 29.47 0.00538 0.00196 + 9 -116.94692 12.19 0.00341 0.00158 + 10 -116.95512 7.04 0.00381 0.00154 + 11 -116.95617 6.39 0.00210 0.00090 + 12 -116.95673 6.03 0.00106 0.00056 + 13 -116.95721 5.73 0.00058 0.00031 + 14 -116.95763 5.46 0.00035 0.00018 + 15 -116.95794 5.28 0.00017 0.00009 + 16 -116.95805 5.20 0.00014 0.00004 +---------- +STATISTICS +---------- + +For the individual parts of the NEB, NEB-CI or NEB-TS run: + +Number of iterations: + Total ... 62 + Reactant and product optimization ... 13 21.0% + NEB ... 35 56.5% + TS optimization ... 14 22.6% +Number of SCF / gradient calculations: + Total ... 704 + Reactant and product optimization ... 13 1.8% + NEB ... 677 96.2% + TS optimization ... 14 2.0% + +---------- + TIMINGS +---------- + +For the individual parts of the NEB, NEB-CI or NEB-TS run: + +Total ... 939.675 sec +Reactant and product optimization ... 102.639 sec 10.9% +NEB ... 749.852 sec 79.8% +TS Optimization ... 87.184 sec 9.3% + + + + ************************************************************ + * Program running with 8 parallel MPI-processes * + * working on a common directory * + ************************************************************ + +------------------------------------------------------------------------------ + ORCA PROPERTY CALCULATIONS +------------------------------------------------------------------------------ + +GBWName ... input.gbw +Number of atoms ... 10 +Number of basis functions ... 22 +Max core memory ... 1792 MB + +Electric properties: +Dipole moment ... YES +Quadrupole moment ... NO +Static polarizability (Dipole/Dipole) ... NO +Static polarizability (Dipole/Quad.) ... NO +Static polarizability (Quad./Quad.) ... NO +Static polarizability (Velocity) ... NO + +Atomic electric properties: +Dipole moment ... NO +Quadrupole moment ... NO +Static polarizability ... NO + +Choice of electric origin ... Center of mass +Position of electric origin ... -0.095025 0.078918 -0.050890 + +General magnetic properties: +Magnetizability ... NO + +EPR properties: +g-Tensor (aka g-matrix) ... NO +Zero-Field splitting spin-orbit ... NO +Zero-field splitting spin-spin ... NO +Hyperfine couplings ... NO ( 0 nuclei) +Quadrupole couplings ... NO ( 0 nuclei) +Contact density ... NO ( 0 nuclei) + +NMR properties: +Chemical shifts ... NO ( 0 nuclei) +Spin-rotation constants ... NO ( 0 nuclei) +Spin-spin couplings ... NO ( 0 nuclei, 0 pairs) + +Choice of magnetic origin ... GIAO +Position of magnetic origin ... 0.000000 0.000000 0.000000 + +Properties with geometric perturbations: +SCF Hessian ... NO +IR spectrum ... NO +VCD spectrum ... NO +X-ray spectroscopy properties: +SCF XES/XAS/RIXS spectra ... NO + + +------------- +DIPOLE MOMENT +------------- + +Method : SCF +Type of density : Electron Density +Multiplicity : 2 +Irrep : 0 +Energy : -116.8648006042969598 Eh +Relativity type : +Basis : AO + X Y Z +Electronic contribution: -0.480331811 0.494764798 -0.155318742 +Nuclear contribution : 0.514982880 -0.427691292 0.275795698 + ----------------------------------------- +Total Dipole Moment : 0.034651069 0.067073506 0.120476956 + ----------------------------------------- +Magnitude (a.u.) : 0.142176822 +Magnitude (Debye) : 0.361384762 + + + +-------------------- +Rotational spectrum +-------------------- + +Rotational constants in cm-1: 1.224753 0.273312 0.243089 +Rotational constants in MHz : 36717.168251 8193.700057 7287.613331 + +Dipole components along the rotational axes: +x,y,z [a.u.] : 0.021099 -0.026452 0.138092 +x,y,z [Debye]: 0.053630 -0.067236 0.351002 + + + +Dipole moment calculation done in 0.0 sec + +Maximum memory used throughout the entire PROP-calculation: 4.6 MB + +-------------------------------- +SUGGESTED CITATIONS FOR THIS RUN +-------------------------------- + +Below you find a list of papers that are relevant to this ORCA run +We neither can nor want to force you to cite these papers, but we appreciate if you do +You receive ORCA, which is the product of decades of hard work by many enthusiastic individuals, for free +The only thing we kindly ask in return is that you cite our papers, +We deeply appreciate it, if you show your appreciation for ORCA by not just citing the generic ORCA reference. + +Please note that relegating all ORCA citations to the supporting information does *not* help us. +SI sections are not indexed - citations you put there will not count into any citation statistics +But we need these citations in order to attract the funding resources that allow us to do what we are doing + +Therefore, if you are a happy ORCA user, please consider citing a few of the papers listed below in the main body of your paper + +In addition to the list printed below, the program has created the file input.bibtex that contains the list in bibtex format +You can import this file easily into all common literature databanks and citation aid programs + + +List of essential papers. We consider these as the minimum necessary citations + + 1. Neese,F. + Software update: the ORCA program system, version 5.0 + WIRES Comput. Molec. Sci., 2022 12(1)e1606 + doi.org/10.1002/wcms.1606 + +List of papers to cite with high priority. The work reported in these papers was absolutely +necessary for this run to complete. +Our perspective: the developers of density functionals and basis sets usually get cited in chemistry papers +Good! But without the algorithms to do something with them, the functionals or basis sets would not do anything. +Hence, in our opinion, the algorithm design and method developments papers are equally worthy of getting cited + + 1. Neese,F. + An improvement of the resolution of the identity approximation for the formation of the Coulomb matrix + J. Comp. Chem., 2003 24(14)1740-1747 + doi.org/10.1002/jcc.10318 + 2. Neese,F.; Wennmohs,F.; Hansen,A.; Becker,U. + Efficient, approximate and parallel Hartree-Fock and hybrid DFT calculations. A 'chain-of-spheres' algorithm for the Hartree-Fock exchange + Chem. Phys., 2009 356(1-3)98-109 + doi.org/10.1016/j.chemphys.2008.10.036 + 3. Asgeirsson,V.; Orri Birgisson,B.; Björnsson,R.; Becker,U.; Neese,F.; Riplinger,C.; Jonsson,H. + Nudged Elastic Band Method for Molecular Reactions Using Energy-Weighted Springs Combined with Eigenvector Following + J. Chem. Theory Comput., 2021 17 4929-4945 + doi.org/10.1021/acs.jctc.1c00462 + 4. Helmich-Paris,B.; de Souza,B.; Neese,F.; Izsák,R. + An improved chain of spheres for exchange algorithm + J. Chem. Phys., 2021 155 104109 + doi.org/doi: 10.1063/5.0058766. + 5. Neese,F. + The SHARK Integral Generation and Digestion System + J. Comp. Chem., 2022 1-16 + doi.org/10.1002/jcc.26942 + +List of suggested additional citations. These are papers that are important in the 'surrounding' of +of this run, or papers that preceded the highly important papers. If you like your results we are grateful for a citation. + + 1. Izsak,R.; Neese,F. + An overlap fitted chain of spheres exchange method + J. Chem. Phys., 2011 135 144105 + doi.org/10.1063/1.3646921 + 2. Izsak,R.; Hansen,A.; Neese,F. + The resolution of identity and chain of spheres approximations for the LPNO-CCSD singles Fock term + Molec. Phys., 2012 110 2413-2417 + doi.org/10.1080/00268976.2012.687466 + 3. Neese,F. + The ORCA program system + WIRES Comput. Molec. Sci., 2012 2(1)73-78 + doi.org/10.1002/wcms.81 + 4. Izsak,R.; Neese,F.; Klopper,W. + Robust fitting techniques in the chain of spheres approximation to the Fock exchange: The role of the complementary space + J. Chem. Phys., 2013 139 + doi.org/10.1063/1.4819264 + 5. Neese,F. + Software update: the ORCA program system, version 4.0 + WIRES Comput. Molec. Sci., 2018 8(1)1-6 + doi.org/10.1002/wcms.1327 + 6. Neese,F.; Wennmohs,F.; Becker,U.; Riplinger,C. + The ORCA quantum chemistry program package + J. Chem. Phys., 2020 152 Art. No. L224108 + doi.org/10.1063/5.0004608 + +List of optional additional citations + + 1. Neese,F. + Approximate second-order SCF convergence for spin unrestricted wavefunctions + Chem. Phys. Lett., 2000 325(1-3)93-98 + doi.org/10.1016/s0009-2614(00)00662-x + +Timings for individual modules: + +Sum of individual times ... 928.464 sec (= 15.474 min) +Startup calculation ... 41.720 sec (= 0.695 min) 4.5 % +SCF iterations ... 88.550 sec (= 1.476 min) 9.5 % +Property calculations ... 0.950 sec (= 0.016 min) 0.1 % +SCF Gradient evaluation ... 47.194 sec (= 0.787 min) 5.1 % +Geometry relaxation ... 0.198 sec (= 0.003 min) 0.0 % +NEB Iterations ... 749.852 sec (= 12.498 min) 80.8 % + ****ORCA TERMINATED NORMALLY**** +TOTAL RUN TIME: 0 days 0 hours 15 minutes 42 seconds 419 msec From 45434835bd819d95064b2229a3eb5308a32a3f16 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Tue, 24 Feb 2026 13:26:03 +0200 Subject: [PATCH 12/13] added neb to main test --- arc/main_test.py | 1 + 1 file changed, 1 insertion(+) diff --git a/arc/main_test.py b/arc/main_test.py index 31d8f3328c..8251079306 100644 --- a/arc/main_test.py +++ b/arc/main_test.py @@ -85,6 +85,7 @@ def test_as_dict(self): 'onedmin': ['server1'], 'openbabel': ['local'], 'orca': ['local'], + 'orca_neb': ['local'], 'qchem': ['server1'], 'terachem': ['server1'], 'torchani': ['local'], From b83b4050c32b20f3d08fe1742474af1eebac2789 Mon Sep 17 00:00:00 2001 From: kfir4444 Date: Tue, 24 Feb 2026 13:26:23 +0200 Subject: [PATCH 13/13] added neb to check_ess_settings, for testing --- arc/common.py | 2 +- 1 file changed, 1 insertion(+), 1 deletion(-) diff --git a/arc/common.py b/arc/common.py index d1224b91fa..8786357c22 100644 --- a/arc/common.py +++ b/arc/common.py @@ -141,7 +141,7 @@ def check_ess_settings(ess_settings: Optional[dict] = None) -> dict: f'strings. Got: {server_list} which is a {type(server_list)}') # run checks: for ess, server_list in settings_dict.items(): - if ess.lower() not in supported_ess + ['gcn', 'heuristics', 'autotst', 'kinbot', 'xtb_gsm']: + if ess.lower() not in supported_ess + ['gcn', 'heuristics', 'autotst', 'kinbot', 'xtb_gsm', 'orca_neb']: raise SettingsError(f'Recognized ESS software are {supported_ess}. Got: {ess}') for server in server_list: if not isinstance(server, bool) and server.lower() not in [s.lower() for s in servers.keys()]: