Complex Franck—Condon overlap integral in nonradiative decays

Abstract

Considering the nuclear coordinate ( Q ) dependence of the electronic energy denominator appearing in the virbonic coupling matrix element, a complex Franck—Condon overlap integral which is needed in order to evaluate the nonradiative decay rate constant not only in the weak coupling but also in the strong coupling case is derived. The real part of the overlap integral plays an important role in the weak coupling case. The imaginary part is originated from the potential energy surface crossing regions and, consequently, contributes to the nonradiative decay rate constant in the strong coupling case. When the Q -dependence of the electronic energy denominator is neglected, the complex overlap integral leads to the results ontained by using the usual Herzberg—Teller expansion method. It is shown that the complex integral is expressed by the optical Franck—Condon overlap integral multiplied by a correction factor when the nonradiative decay from the vibrationless state is considered.