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Title: Transition state theory for activated systems with driven anharmonic barriers
Authors: Revuelta, F.
Craven, Galen T.
Bartsch, Thomas
Borondo, F.
Benito, R.M.
Hernandez, Rigoberto
Issue Date: 2017
Publisher: AIP Publishing
Citation: REVUELTA, F. ...et al., 2017. Transition state theory for activated systems with driven anharmonic barriers. Journal of Chemical Physics, 147: 074104.
Abstract: 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.
Description: 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.
Sponsor: 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.
Version: Accepted for publication
DOI: 10.1063/1.4997571
URI: https://dspace.lboro.ac.uk/2134/26256
Publisher Link: http://dx.doi.org/10.1063/1.4997571
ISSN: 0021-9606
Appears in Collections:Published Articles (Physics)

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