Electron Transfer Between Self Trapped (Solitary) States

Abstract

A model for electron transfer is presented. It is based on a selfconsistent treatment of the initial (final)-state charge distribution and the equilibrium arrangements tot the molecular coordinates. The theory comprises the nonadiabatic electron transfer and internal conversion processes as special limits within the same frame. It is shown that the initial state contains a small degree of charge delocalization, which is a resonance like function of the free energy change. It peaks when the free energy change matches the nuclear reorganisation energy. The physical origin for this resonance like enhancement is a non-Condon- effect. The analysis of exact eigenstates for an asymmetric dimer is used to interrelate this soliton approach with others based on the small polaron transformation.