Approximate phase-space transport theory for vibrational predissociation

A. A. Buchachenko, N. F. Stepanov

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9 Citations (Scopus)


Approximate version of the phase-space transport theory for vibrational predissociation of the van der Waals complexes with two degrees of freedom is proposed and tested. The theory uses the concept of phase-space bottlenecks which govern the phase-point stochastic diffusion. The global transport is treated as a sequence of the transitions across the bottlenecks within a kineticlike model. Simplified formulas for the transition probabilities across dissociation separatrix (intermolecular bottleneck) and Golden cantori (intramolecular bottlenecks) are obtained under the zeroth-order approximation. Applications to some model complexes indicate the ability of the model to reproduce correctly individual bottleneck parameters as well as the total predissociation rates. Some observations concerning the multibottleneck kinetic models are discussed.

Original languageEnglish
Pages (from-to)5486-5498
Number of pages13
JournalJournal of Chemical Physics
Issue number7
Publication statusPublished - 1993
Externally publishedYes


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