Application of the density matrix method in the quantum mechanical calculation of the bridge-assisted electron transfer probability in polar media

Abstract

A quantum mechanical method is used to calculate the probability of electron transfer via a bridge species. The calculation shows that the Arrhenius energy exponent is determined by the highest intersection point of the potential energy surface of the intermediate state either with that of the initial or with that of the final state. For suitable relative positions of the various terms, this energy is lower than the energy of the intersection point between potential energy surfaces of the initial and final states, corresponding to a direct electron transfer reaction. Thus the electron transfer processes through bridge systems can be more effective than direct electron transfer.