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Communication: transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields

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posted on 22.05.2015 by Galen T. Craven, Thomas Bartsch, Rigoberto Hernandez
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product—for example, an energy barrier—becomes timedependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez,“Persistence of transition state structure in chemical reactions driven by fields oscillating in time,”Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories

Funding

National Science Foundation (NSF) through Grant No.NSF-CHE-1112067. Travel between partners was partially supported through the People Programme (Marie Curie Actions) of the European Union’s (EU) Seventh Framework Programme FP7/2007-2013/ under REA Grant Agreement No.294974

History

School

  • Science

Department

  • Mathematical Sciences

Published in

JOURNAL OF CHEMICAL PHYSICS

Volume

141

Issue

4

Pages

? - ? (5)

Citation

CRAVEN, G.T., BARTSCH, T. and HERNANDEZ, R., 2014. Communication: transition state trajectory stability determines barrier crossing rates in chemical reactions induced by time-dependent oscillating fields. Journal of Chemical Physics, 141 (4), 041106.

Publisher

© AIP Publishing LLC

Version

VoR (Version of Record)

Publication date

2014

Notes

Copyright (2014) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Journal of Chemical Physics and may be found at http://dx.doi.org/10.1063/1.4891471

ISSN

0021-9606

Language

en

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