Microscopic solvation dynamics and solvent-controlled electron transfer

In this paper we investigate solvent size effects on solvent-controlled electron transfer (ET) in polar liquids. An interrelationship was established between the solvation time correlation function and the ET rate, which was presented within the first passage time approximation. For the case of activationless ET the ET rate, which is equal to the initial solvation rate, was expressed within the framework of the mean spherical approximation. The theory predicts that the activationless ET times are shorter than the average dipole solvation times, in accord with experimental data for intramolecular ET in electronically excited bianthryl in nonassociated polar solvents.