Static and dynamical solvent effects on electron transfer rates

Abstract

The Marcus equation of electron transfer rates is generalized. The rate constant is expressed in terms of the function φ(ΔV) which describes the distribution of the electrostatic potential difference ΔV between donor and acceptor sites, produced by the surrounding fluctuating polar solvent molecules. The static solvent effect on electron transfer is discussed on the basis of this expression. The dynamical solvent effect on electron transfer is also studied to explain the non-Marcus energy gap law recently observed for back electron transfer in contact ion pairs.