Influence of diffusion on the kinetics of excited-state association--dissociation reactions: comparison of theory and simulation

Several recent theories of the kinetics of diffusion influenced excited-state association--dissociation reactions are tested against accurate Brownian dynamics simulation results for a wide range of parameters. The theories include the relaxation time approximation (RTA), multiparticle kernel decoup...

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Bibliographic Details
Published inThe Journal of chemical physics Vol. 120; no. 13; p. 6111
Main Authors Popov, Alexander V, Agmon, Noam, Gopich, Irina V, Szabo, Attila
Format Journal Article
LanguageEnglish
Published United States 01.04.2004
Subjects
Computer Simulation
Diffusion
Energy Transfer
Kinetics
Models, Chemical
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Summary:Several recent theories of the kinetics of diffusion influenced excited-state association--dissociation reactions are tested against accurate Brownian dynamics simulation results for a wide range of parameters. The theories include the relaxation time approximation (RTA), multiparticle kernel decoupling approximations and the so-called kinetic theory. In the irreversible limit, none of these theories reduce to the Smoluchowski result. For the pseudo-first-order target problem, we show how the RTA can be modified so that the resulting formalism does reduce correctly in the irreversible limit. We call this the unified Smoluchowski approximation, because it unites modern theories of reversible reactions with Smoluchowski's theory of irreversible reactions.
ISSN:0021-9606
DOI:10.1063/1.1649935