Non radiative transition probabilities in the statistical limit

In this paper we derive a general computational scheme for the calculation of the non radiative decay probability of a polyatomic molecule in the statistical limit. Within the framework of the Harmonic Approximation the relaxation rate of any polyatomic molecule can be expressed in terms of an infinite sum where each term consists of a medium distribution function and an intramolecular term. In the statistical limit the medium induced vibrational relaxation widths do not affect the non radiative decay characteristics. Numerical calculations are reported for the T ₁S ₀ intersystem crossing in the benzene molecule.