The flux-flux correlation function for anharmonic barriers

Arseni Goussev, Roman Schubert, Holger Waalkens, Stephen Wiggins*

*Corresponding author for this work

    Research output: Contribution to journalArticleAcademicpeer-review

    4 Citations (Scopus)
    354 Downloads (Pure)

    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 for a general f degree-of-freedom system having an index one saddle 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. (C) 2010 American Institute of Physics. [doi:10.1063/1.3518425]

    Original languageEnglish
    Article number244113
    Number of pages8
    JournalJournal of Chemical Physics
    Volume133
    Issue number24
    DOIs
    Publication statusPublished - 28-Dec-2010

    Keywords

    • TRANSITION-STATE THEORY
    • REACTION-RATE CONSTANTS
    • PHASE-SPACE
    • CHEMICAL-REACTIONS
    • NONSEPARABLE SYSTEMS
    • SEMICLASSICAL THEORY
    • QUANTUM-MECHANICS
    • DAMPED SYSTEMS
    • PROBABILITIES
    • CONSTRUCTION

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