Computation of Electron Transfer Rates: The Nonadiabatic Instanton Solution

摘要

A computational theory for determining electron transfer rate constants isformulated based on an instanton expression for the quantum rate and the self-consistent solution of the imaginary time nonadiabatic steepest descent approximation. The theory obtains the correct asymptotic behavior for the electron transfer rate constant in the nonadiabatic cases, and it smoothly bridges between those two limits for intermediate couplings. Furthermore, no assumptions regarding the form of the diabatic states can be included in the calculations. The method thereby holds considerable promise for computing electron transfer rate constants in realistic condensed phase systems.