The Flux-Flux Correlation Function for Anharmonic Barriers

Arseni Goussev, Roman Schubert, Holger Waalkens, Stephen Wiggins

Research output: Contribution to journalArticle (Academic Journal)peer-review

3 Citations (Scopus)

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.
Original languageEnglish
JournalJournal of Chemical Physics
Volume133
Issue number24
DOIs
Publication statusPublished - 28 Dec 2010

Bibliographical note

9 pages, 2 figures

Keywords

  • physics.chem-ph
  • math-ph
  • math.MP
  • nlin.CD
  • quant-ph

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