ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
6 files

Coupled Anharmonic Thermochemistry from Stratified Monte-Carlo Integration

preprint
submitted on 23.02.2021, 09:27 and posted on 24.02.2021, 11:09 by Gabriel Rath, Wassja Kopp, Kai Leonhard
This study presents CIMCI, a new semi-classical method for handling fully coupled anharmonicity in gas-phase thermodynamics that promises to be black-boxable, to be
applicable for all kinds of anharmonicity, and to scale better at higher dimensionality than other methods for handling gas-phase molecular anharmonicity. The method
does so by using automatically and recursively stratified, simultaneous Monte Carlo integration of multiple functions. For the small systems analyzed by this study, the
method’s anharmonic corrections match reference data better than those of other blackbox anharmonic methods, e.g. VPT2. This holds even when sampling with CIMCI
is done with primitive force fields, e.g. UFF, while the competing methods are used with proper, comprehensive potentials, e.g. the M06-2X meta-hybrid DFT functional.
With further refinements in Monte Carlo sampling efficiency, in the quality of fast potentials practical for Monte Carlo sampling, and in automatic detection of which stereoisomers should be included during sampling, CIMCI has the potential to be the ideal anharmonic treatment for larger molecules where the large number of conformers
and the high dimensionality of coupled torsions present major difficulties for other, existing treatments for anharmonicity.

Funding

Automatic generation of Chemical Models

European Commission

Find out more...

History

Email Address of Submitting Author

wassja.kopp@ltt.rwth-aachen.de

Institution

Institute of Technical Thermodynamics, RWTH Aachen University, 52062 Aachen

Country

Germany

ORCID For Submitting Author

0000-0001-8147-3464

Declaration of Conflict of Interest

Gabriel Rath was employed by SCM, a company developing a commercial implementation of the presented code into the Amsterdam Modeling Suite AMS.

Exports