Theoretical and Computational Chemistry

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

Authors

Abstract

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.

Version notes

Minor errors fixed. Initial journal submission.

Content

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