Theory of reversible diffusion-influenced reactions

Noam Agmon*, Attila Szabo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

245 Scopus citations

Abstract

A unified theory of reversible diffusion-influenced geminate and pseudo- first-order reactions is developed. Explicit results are presented for the time dependence of the fraction of molecules that are dissociated at time t for a variety of initial conditions. To introduce the basic ideas of our approach, an elementary and rather complete treatment of the irreversible reaction between a pair of interacting, spherically symmetric particles is presented. The focus is on deriving relations among survival probabilities and bimolecular time-dependent rate coefficients for the radiation and absorbing boundary conditions and the asymptotic behavior of these quantities. These relations are then generalized to reversible geminate reactions. For example, it is shown that the separation probability for an initially bound pair satisfies a simple convolution relation involving the survival probability of an irreversibly reacting geminate pair initially at contact. An analytic expression is obtained for this separation probability that is exact for free diffusion and is an accurate approximation for interacting particles. Finally, the Smoluchowski approach to irreversible pseudo-first-order reactions is extended to reversible reactions. The analysis is based on the generalization of the convolution relations that are rigorously valid for isolated pairs.

Original languageEnglish
Pages (from-to)5270-5284
Number of pages15
JournalThe Journal of Chemical Physics
Volume92
Issue number9
DOIs
StatePublished - 1990

Fingerprint

Dive into the research topics of 'Theory of reversible diffusion-influenced reactions'. Together they form a unique fingerprint.

Cite this