Smoluchowski Theory as the Leading Term of Reversible Geminate Dissociation Kinetics

A. V. Popov, N. Agmon*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The significance of the Smoluchowski theory transcends its initial goal of depicting pseudo-unimolecular irreversible kinetics. We show that a generalized Smoluchowski theory (GST) provides a short-time description for reversible geminate dissociation reactions even in the presence of a potential of interaction. Using this property, we succeed in constructing an excellent approximation for the whole time dependence, in which the GST is the leading term. We discuss the implication of these observations to experimental data, particularly for excited-state proton transfer to solvent.

Original languageEnglish
Pages (from-to)1659-1668
Number of pages10
JournalPolish Journal of Chemistry
Volume77
Issue number11
StatePublished - Nov 2003

Keywords

  • Diffusion
  • Geminate recombination
  • Reversible kinetics
  • Smoluchowski theory

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