The general treatment of superexchange versus sequential electron transfer in a three-component system

Abstract
The mechanisms of superexchange vs sequential electron transfer in a three‐component system involving reactant, intermediate, and product are investigated by using the Zusman equation. This approach is nonperturbative with regard to the electronic coupling and thus, in principle, the contributions from all higher order terms are included. This treatment allows examination of a wide range of conditions from nondegenerate to degenerate cases, as well as from nonadiabatic to adiabatic cases for electron transfer processes involving three Marcus parabolas such as believed to occur in photosynthetic reaction centers. New effects of superexchange on electron‐transfer rate resulting from degenerate energy‐level crossings are predicted.

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