ROLE OF SOLVENT ELECTRONIC POLARIZATION IN ELECTRON-TRANSFER PROCESSES

The role of solvent electronic polarization in electron-transfer processes is investigated. The solvent electronic polarization is assumed to be instantaneously equilibrated to the quantum charge distribution of the transferring electron and the fluctuating solvent orientational polarization; this yields a nonlinear Schrödinger equation for the electron wave function. The transition between nonadiabatic and adiabatic regimes is found to be governed by both electronic coupling and electronic polarization. Activation and reorganization free energies are obtained; in some regimes, they differ considerably from some conventional predictions. The physical origin and consequences of these features are described. © 1990 American Chemical Society.