Quantum/classical studies of photo dissociation and reaction dynamics in clusters

Abstract

In this paper, a multiple configurational time-dependent self-consistent field (TDSCF) approach for studying photodissociation and reaction dynamics is described. This approach has been applied to studies of several benchmark systems and is found to provide an accurate description of the reactions. The focus of the present work is on investigations of processes in cluster environments. Specifically, the dynamics of the O(³P) + HCl reaction and H₂O photodissociation dynamics in isolation and in Van der Waals complexes with one argon atom are compared. The nature and importance of quantum mechanical effects in these systems are investigated through an analysis of the results of the quantum/classical simulations and a comparison of these results with those obtained from previously reported experimental and classical studies on these systems. It is found that, although the effects of complexation are subtle, they are not negligible. In addition, most of them can be understood in terms of kinematic and steric factors, although electronic effects cannot be dismissed.