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J Chem Phys. 2017 Oct 28;147(16):161701. doi: 10.1063/1.4979712.

Cheap but accurate calculation of chemical reaction rate constants from ab initio data, via system-specific, black-box force fields.

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Institut für Physikalische Chemie, Christian-Albrechts-Universität, Olshausenstraße 40, D-24098 Kiel, Germany.


Building on the recently published quantum-mechanically derived force field (QMDFF) and its empirical valence bond extension, EVB-QMDFF, it is now possible to generate a reliable potential energy surface for any given elementary reaction step in an essentially black box manner. This requires a limited and pre-defined set of reference data near the reaction path and generates an accurate approximation of the reference potential energy surface, on and off the reaction path. This intermediate representation can be used to generate reaction rate data, with far better accuracy and reliability than with traditional approaches based on transition state theory (TST) or variational extensions thereof (VTST), even if those include sophisticated tunneling corrections. However, the additional expense at the reference level remains very modest. We demonstrate all this for three arbitrarily chosen example reactions.


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