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Reaction rate calculation with time-dependent invariant manifolds

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posted on 10.09.2014 by Thomas Bartsch, F. Revuelta, R.M. Benito, F. Borondo
The identification of trajectories that contribute to the reaction rate is the crucial dynamical ingredient in any classical chemical reactivity calculation. This problem often requires a full scale numerical simulation of the dynamics, in particular if the reactive system is exposed to the influence of a heat bath. As an efficient alternative, we propose here to compute invariant surfaces in the phase space of the reactive system that separate reactive from nonreactive trajectories. The location of these invariant manifolds depends both on time and on the realization of the driving force exerted by the bath. These manifolds allow the identification of reactive trajectories simply from their initial conditions, without the need of any further simulation. In this paper, we show how these invariant manifolds can be calculated, and used in a formally exact reaction rate calculation based on perturbation theory for any multidimensional potential coupled to a noisy environment.

Funding

This work has been supported by the MCINN (Spain) under projects MTM2009-14621 and CONSOLIDER 2006-32 (i-Math). F.R. gratefully acknowledges a doctoral fellowship the UPM and the hospitality of the members of the School of Mathematics at Loughborough University, where part of this work was done.

History

School

  • Science

Department

  • Mathematical Sciences

Published in

JOURNAL OF CHEMICAL PHYSICS

Volume

136

Issue

22

Pages

? - ? (17)

Citation

BARTSCH, T. ... et al., 2012. Reaction rate calculation with time-dependent invariant manifolds. Journal of Chemical Physics, 136 (22), 17pp.

Publisher

© American Institute of Physics

Version

VoR (Version of Record)

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/

Publication date

2012

Notes

This article was published in the Journal of Chemical Physics [© American Institute of Physics] and the definitive version is also available from: http://dx.doi.org/10.1063/1.4726125

ISSN

0021-9606

Language

en

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