Energy dependence of nonradiative decay in polyatomic molecules^†

A theory is presented to describe the dependence of nonradiative decay rates of polyatomic molecules upon the initially selected vibronic states. In the large molecule statistical limit it is demonstrated that it is possible to assign vibrational frequencies in an electronic state by measuring nonradiative decay rates into that electronic state. After discussing the inadequacies of other theories, a discussion is presented of the richness of phenomena that are expected to arise from the energy dependence of nonradiative decay rates in polyatomic molecules.