A time-dependent approach to the intramolecular vibrational relaxation mechanism. An application to the Ar...Cl2(B) complex

Abstract

In this paper, a time-dependent and a time-independent formalism based on the diabatic configuration interaction (DCI) are presented as a way of studying the intramolecular vibrational relaxation (IVR) phenomenon in the Ar...Cl2 van der Waals complex. Both formalism show the importance of the mixing of different vibrational states in the metastable initial wavefunction, mainly of the v + 1 and v-1 channels. By so doing, the IVR is explained by means of a pure quantal interference mechanism. © 1990.