Abstract

Theory for nonadiabatic electron-transfer reactions at high temperature is presented for a three-component system (a donor, an acceptor, and a bridging intermediate). Only the ``degenerate`` regime of triple energy-level crossing is considered assuming three Marcus parabolas cross at the same point and the direct free energy gap vanishes. Because the ordinary second-order perturbation theory fails, the nonperturbative stochastic Liouville approach of Zusman is used in deriving analytical expressions for the superexchange and the sequential electron-transfer rate constants.

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