Quantum/classical studies of photodissociation and reaction dynamics in clusters

In this paper, a multiple configurational time-dependent self-consistent fi eld (TDSCF) approach for studying photodissociation and reaction dynamics i s 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(P-3) + HCl reaction and H 2O photodissociation dynamics in isolation and in Van der Waals complexes w ith one argon atom are compared. The nature and importance of quantum mecha nical effects in these systems are investigated through an analysis of the results of the quantum/classical simulations and a comparison of these resu lts with those obtained from previously reported experimental and classical studies on these systems. It is found that, although the effects of comple xation are subtle, they are not negligible. In addition, most of them can b e understood in terms of kinematic and steric factors, although electronic effects cannot be dismissed.