ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
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,E) 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.456048
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