Erratum: Dynamics of reversible electron transfer reactions [J. Chem. Phys. 95, 3325 (1991)] (original) (raw)

1992, Journal of Chemical Physics

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Dynamics of reversible electron transfer reactions

The Journal of Chemical Physics, 1991

The dynamics of reversible electron transfer reactions in Debye solvents are studied by employing two coupled diffusion–reaction equations with the rate constants depending on the reaction coordinate. The equations are solved analytically in four limiting cases: fast and slow reactions as well as wide and narrow reaction windows. A general solution for the survival probabilities is obtained by employing a decoupling approximation similar to the one used by Sumi and Marcus [J. Chem. Phys. 84, 4896 (1986)] for nonreversible reactions; our solution verifies the existence of four limiting cases and also predicts the behavior between these limits. Interpolation between long and short time approximations to the general solution, leads to survival probabilities with a single exponential time dependence and rate constants ki satisfying the relation k1/k2=exp(−βΔG0), where ΔG0 is the standard free energy change for the reaction. Multiexponential behavior of the survival probabilities is exhi...

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