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Advances in Automated Transition State Theory Calculations: Improvements on the AutoTST Framework

preprint
revised on 04.12.2020, 21:26 and posted on 07.12.2020, 10:03 by Nathan Harms, Carl Underkoffler, Richard West
Kinetic modeling of combustion chemistry has made substantial progress in recent years with the development of increasingly detailed models. However, many of the chemical kinetic parameters utilized in detailed models are estimated, often inaccurately. To help replace rate estimates with more accurate calculations, we have developed AutoTST, an automated Transition State Theory rate calculator. This work describes improvements to AutoTST, including: a systematic conformer search to find an ensemble of low energy conformers, vibrational analysis to validate transition state geometries, more accurate symmetry number calculations, and a hindered rotor treatment when deriving kinetics. These improvements resulted in location of transition state geometry for 93% of cases and generation of kinetic parameters for 74% of cases. Newly calculated parameters agree well with benchmark calculations and perform well when used to replace estimated parameters in a detailed kinetic model of methanol combustion.

Funding

Resolving discrepancies in detailed kinetic models of combustion via automated transition state theory calculations

Directorate for Engineering

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CDS&E: Collaborative Research: Autonomous Systems for Experimental and Computational Data Generation and Data-Driven Modeling of Combustion Kinetics

Directorate for Engineering

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U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award #0000232253, as part of the Computational Chemical Sciences Program.

History

Email Address of Submitting Author

r.west@northeastern.edu

Institution

Northeastern University

Country

USA

ORCID For Submitting Author

0000-0003-3861-6030

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Minor errors fixed. Initial journal submission.

Exports