Theory of intramolecular vibrational relaxation in large systems

Abstract

A general theory for intramolecular vibrational relaxation is proposed. The theory provides a master equation, analogous to the Pauli master equation in non-equilibrium statistical mechanics, for this process. The master equation contains a completely general time independent perturbation operator, which causes the system to relax to equilibrium. The choice of the three-phonon interaction operator as a perturbation is treated in detail, and a comparison with experimental data is made.