Transition state theory for activated systems with driven anharmonic barriers

Revuelta Peña, Fabio and Craven, Gaten T. and Bartsch, Thomas and Borondo Rodríguez, Florentino and Benito Zafrilla, Rosa Maria (2017). Transition state theory for activated systems with driven anharmonic barriers. "The Journal of Chemical Physics", v. 147 (n. 7); pp.. ISSN 0021-9606. https://doi.org/10.1063/1.4997571.

Description

Title: Transition state theory for activated systems with driven anharmonic barriers
Author/s:
  • Revuelta Peña, Fabio
  • Craven, Gaten T.
  • Bartsch, Thomas
  • Borondo Rodríguez, Florentino
  • Benito Zafrilla, Rosa Maria
Item Type: Article
Título de Revista/Publicación: The Journal of Chemical Physics
Date: August 2017
Volume: 147
Subjects:
Faculty: E.T.S. de Ingeniería Agronómica, Alimentaria y de Biosistemas (UPM)
Department: Ingeniería Agroforestal
Creative Commons Licenses: Recognition - No derivative works - Non commercial

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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 per- turbative 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 oscil- latory 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 expo- nents, 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 Projects

TypeCodeAcronymLeaderTitle
Government of SpainMTM2015-63914-PUnspecifiedUnspecifiedUnspecified
Horizon 2020734557TraXUnspecifiedStability and Transitions in Physical Processes

More information

Item ID: 47764
DC Identifier: http://oa.upm.es/47764/
OAI Identifier: oai:oa.upm.es:47764
DOI: 10.1063/1.4997571
Official URL: http://aip.scitation.org/doi/abs/10.1063/1.4997571
Deposited by: Memoria Investigacion
Deposited on: 08 Nov 2017 09:08
Last Modified: 14 Mar 2019 13:49
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