title: Influence of diffusion on the kinetics of excited-state association--dissociation reactions: comparison of theory and simulation.
abstract: 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.
authors.affiliation: Department of Physical Chemistry and the Fritz Haber Research Center, The Hebrew University, Jerusalem 91904, Israel.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Popov
authors.forename: Noam
authors.initials: N
authors.lastname: Agmon
authors.forename: Irina V
authors.initials: IV
authors.lastname: Gopich
authors.forename: Attila
authors.initials: A
authors.lastname: Szabo
mesh_terms: D003198:Computer Simulation; D004058:Diffusion; D004735:Energy Transfer; D007700:Kinetics; D008956:Models, Chemical