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Influence of diffusion on the kinetics of excited-state associationdissociation reactions: Comparison of theory and simulation

Summary: Influence of diffusion on the kinetics of excited-state
association­dissociation reactions: Comparison of theory and simulation
Alexander V. Popova)
and Noam Agmon
Department of Physical Chemistry and the Fritz Haber Research Center, The Hebrew University,
Jerusalem 91904, Israel
Irina V. Gopichb)
and Attila Szabo
Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases,
National Institutes of Health, Bethesda, Maryland 20892
Received 11 November 2003; accepted 31 December 2003
Several recent theories of the kinetics of diffusion influenced excited-state association­dissociation
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. © 2004 American
Institute of Physics. DOI: 10.1063/1.1649935


Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem


Collections: Chemistry