Adiabatic representations for the study of flux redistribution during photodissociation involving coupled electronic states: The effect of vibrational excitation on the photofragmentation of CH3I

Abstract

In this paper we exploit a method for the time-independent study of the growth of photofragment flux, governed by photon absorption, and the subsequent redistribution of the flux, governed by the Hamiltonian in the excited, unbound state. For dissociation involving multiple electronic states, each with internal (vibrational or rovibrational) degrees of freedom, from a mechanistic standpoint it is more revealing to analyze the flux in a basis which is adiabatic in the nuclear degrees of freedom but diabatic in the electronic degrees of freedom. This approach is pursued here in application to a two-dimensional model for the photodissociation of CH3I.