THE RATE OF ELECTRON-TRANSFER REACTIONS IN THE DIFFUSIVE LIMIT
Author(s): W.Schmickler (Abteilung Elektrochemie, University of Ulm, D-89069 Ulm, Germany)
A simple electron-transfer reaction is treated in the diffusive limit, in which the motion of the solvent is governed by the Smoluchowski equation. The electronic transition probability is calculated from the Landau-Zener expression. The rate constant of the reaction is calculated as a function of the strength of the electronic interaction between the reactants. For weak interactions, the rate is the same as that obtained form first-order perturbation theory. For strong interactions, solvent dynamics is rate-determining. The calculations presented here bridge these two limits.
Key words: electron transfer reactions, diffusive limit
PACS: 82.30.F, 82.20.Gk
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