Quantum dynamics of the photoinitiated unimolecular dissociation of HOCO

Abstract

The photodissociation dynamics of HOCO in the overtone νOH=3 are studied using a time-dependent wave packet dynamics approach. The dynamics calculations are carried out using a four-dimensional planar model in which the terminal C=O bond (spectator) is fixed at its equilibrium bond distance in the trans-HOCO conformer based on an empirical potential energy surface for HOCO fit to accurate ab initio calculations of the stationary point energies. The branching fraction into the H+CO2 products, and the resonance states associated with νOH=3 are investigated in detail.