1605.03339.pdf (2.34 MB)
Transition state theory for solvated reactions beyond recrossing-free dividing surfaces
journal contribution
posted on 2016-06-10, 13:14 authored by F. Revuelta, Thomas BartschThomas Bartsch, P.L. Garcia-Muller, Rigoberto Hernandez, R.M. Benito, F. BorondoThe 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. EVolume
93Issue
6Citation
REVUELTA, F. ...et al., 2016. Transition State Theory for solvated reactions beyond recrossing-free dividing surfaces. Physical Review E, 93, 062304.Publisher
© American Physical SocietyVersion
- 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
2016-05-11Publication date
2016-06-06Notes
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.93.062304ISSN
1539-3755eISSN
1550-2376Publisher version
Language
- en