The flux-flux correlation function for anharmonic barriers

Goussev, Arseni, Schubert, Roman, Waalkens, Holger and Wiggins, Stephen (2010) The flux-flux correlation function for anharmonic barriers. The Journal of Chemical Physics, 133 (24). p. 244113. ISSN 0021-9606

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Official URL: http://dx.doi.org/10.1063/1.3518425

Abstract

The flux-flux correlation function formalism is a standard and widely used approach for the computation of reaction rates. In this paper we introduce a method to compute the classical and quantum flux-flux correlation functions for anharmonic barriers essentially analytically through the use of the classical and quantum normal forms. In the quantum case we show that the quantum normal form reduces the computation of the flux-flux correlation function to that of an effective one dimensional anharmonic barrier. The example of the computation of the quantum flux-flux correlation function for a fourth order anharmonic barrier is worked out in detail, and we present an analytical expression for the quantum mechanical microcanonical flux-flux correlation function. We then give a discussion of the short-time and harmonic limits.

Item Type: Article
Subjects: F100 Chemistry
F300 Physics
G100 Mathematics
Department: Faculties > Engineering and Environment > Mathematics and Information Sciences
Depositing User: Arseni Goussev
Date Deposited: 22 Oct 2012 11:34
Last Modified: 13 May 2017 16:49
URI: http://nrl.northumbria.ac.uk/id/eprint/9855

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