Dynamics of inner- and outer-sphere electron transfer in a polar solvent

In this paper, inner-sphere electron transfer reactions in a solvent are studied in the framework of multidimensional transition state theory. It is demonstrated that the preexponential factor essentially depends upon the interaction with the inner-sphere vibrational mode, increasing the rate of electron transfer as much as one order of magnitude. The prefactor is shown to be strongly dependent on the frequency of this vibration. At high frequencies the rate constant increases with the reorganization energy of this inner-sphere mode while at small frequencies, electron transfer is inhibited. Estimations of inner mode reorganization energies have been performed for system where it is necessary to account nonequilibrium solvent relaxation. Finally it is shown that the equilibrium approximation fails when the reaction is close to an activationless regime.