Boltzmann statistics and radiationless decay in large molecules: Optical selection studies

We elaborate upon the conceptual value of a recent formulation of the theory of radiationless transitions, and determine the dependence of the nonradiative rate constant on excess vibrational energy in the excited electronic state. Measurements of the lifetimes of benzene excited to individual vibronic states are reported. Cur rough numerical calculations are found to be consistent with the experimental data.