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Transition state theory for activated systems with driven anharmonic barriers

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posted on 25.08.2017 by F. Revuelta, Galen T. Craven, Thomas Bartsch, F. Borondo, R.M. Benito, Rigoberto Hernandez
Classical transition state theory has been extended to address chemical reactions across barriers that are driven and anharmonic. This resolves a challenge to the naive theory that necessarily leads to recrossings and approximate rates because it relies on a fixed dividing surface. We develop both perturbative and numerical methods for the computation of a time-dependent recrossing-free dividing surface for a model anharmonic system in a solvated environment that interacts strongly with an oscillatory external field. We extend our previous work, which relied either on a harmonic approximation or on periodic force driving.We demonstrate that the reaction rate, expressed as the long-time flux of reactive trajectories, can be extracted directly from the stability exponents, namely, Lyapunov exponents, of the moving dividing surface. Comparison to numerical results demonstrates the accuracy and robustness of this approach for the computation of optimal (recrossing-free) dividing surfaces and reaction rates in systems with Markovian solvation forces. The resulting reaction rates are in strong agreement with those determined from the long-time flux of reactive trajectories.

Funding

Thiswork has been partially supported by the the National Science Foundation (NSF) (USA) through Grant No. CHE-1700749, the Ministry of Economy and Competitiveness (MINECO, Spain) under Contract No. MTM2015-63914-P, and by ICMAT Severo Ochoa under Contract No. SEV-2015-0554.

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  • Science

Department

  • Physics

Published in

Journal of Chemical Physics

Citation

REVUELTA, F. ...et al., 2017. Transition state theory for activated systems with driven anharmonic barriers. Journal of Chemical Physics, 147: 074104.

Publisher

AIP Publishing

Version

VoR (Version of Record)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Acceptance date

19/07/2017

Publication date

2017

Notes

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in REVUELTA, F. ...et al., 2017. Transition state theory for activated systems with driven anharmonic barriers. Journal of Chemical Physics, 147: 074104. and may be found at http://dx.doi.org/10.1063/1.4997571.

ISSN

0021-9606

Language

en

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