Sensitivity of unimolecular lifetime distributions and energy dependent rate constants to fluctuations in state specific rate constants

Da Hong Lu, William L. Hase

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

Different distribution functions are used to describe fluctuations in state-specific unimolecular rate constants, for states which lie within a narrow energy interval. The effect of these distributions on the reactant population vs time N(τ,S) and the time-dependent unimolecular rate constant k(τ,E) are considered. Comparisons are made with the exponential decay predicts by RRKM (Rice-Ramsperger-Kassel-Marcus) theory of unimolecular kinetics. The collision-averaged unimolecular rate constant k(ω,E) is also determined for each of the distributions of state-specific unimolecular rate constants. Overall, k(ω,E) is found to be relatively insensitive to fluctuations in state-specific unimolecular rate constants.

Original languageEnglish
Pages (from-to)1557-1563
Number of pages7
JournalThe Journal of Chemical Physics
Volume90
Issue number3
DOIs
StatePublished - 1989

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