The Calculation of the Rates of Intramolecular Nonradiative Transitions in Benzene

Abstract

Abstract Intramolecular nonradiative transition rates for various interstates of benzene were calculated from the standpoint of the breakdown of the Born-Oppenheimer approximation. The electronic parts of the coupling matrix elements were explicitly evaluated. These parts vary in the range of 10−1–10−3 Å−1. The nonradiative transition rates for the 1E1u→1B1u,1B2u transitions were predicted to be appreciable. The rate for the 1B1u→1B2u transition vanishes as long as the geometrical structure of the 1B1u state is assumed to be of the D6h symmetry. These results are compared with the experimental nonradiative transition widths recently reported by Jortner et al.