Effects of anharmonicity and electronic coupling on photoinduced electron transfer in mixed valence compounds

We develop a semigroup model of electron transfer (ET) dynamics in mixed valence compounds. This model is useful for investigating the effects of anharmonicity in inner sphere nuclear modes, as well as the dependence of the electronic dynamics on the nature of the electronic coupling. Two effective "subsystem" nuclear vibrations are treated explicitly in the model, to account for the rapid electronic energy gap fluctuations induced by the inner sphere vibrations. The essentially Markovian effects of the remaining "bath" modes are approximated by semigroups. We find that including the anharmonicity in inner sphere vibrations leads to a very small increase in the rate of ET. This effect is due to the change in reactant and product vibronic states when anharmonicity is included, as well as the rapid electronic dephasing induced by the bath. An assumption of strong electronic coupling is found to be sufficient to explain experimentally observed ET rates, but the possible role of conical intersections in ultrafast ET reactions is also noted. (C) 2002 American Institute of Physics.