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Transition state theory for solvated reactions beyond recrossing-free dividing surfaces

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posted on 10.06.2016 by F. Revuelta, Thomas Bartsch, P.L. Garcia-Muller, Rigoberto Hernandez, R.M. Benito, F. Borondo
The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing-free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non-Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmonic potential barrier. The excellent performance of our method is illustrated with an application to a realistic model for isomerization.

Funding

This work was funded by the Ministerio de Economia y Competitividad (Spain) under Contracts No. MTM2012-39101 and MTM2015-63914-P, and ICMAT Severo Ochoa SEV5 2011-0087 and SEV-2015-0554

History

School

  • Science

Department

  • Mathematical Sciences

Published in

Phys. Rev. E

Volume

93

Issue

6

Citation

REVUELTA, F. ...et al., 2016. Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces. Physical Review E, 93, 062304.

Publisher

© American Physical Society

Version

AM (Accepted Manuscript)

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

11/05/2016

Publication date

2016-06-06

Notes

This paper was accepted for publication in the journal Physical Review E and the definitive published version is available at http://dx.doi.org/10.1103/PhysRevE.93.062304

ISSN

1539-3755

eISSN

1550-2376

Language

en

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