Hybrid quantum/classical simulation and kinetic study of the vibrational predissociation of Cl_2 ... Ne_n (n = 2,3)

摘要

A hybrid quantum/classical method is applied to the vibrational predissociation of van der Waals clusters containing a diatomic molecule and several rare gas atoms, Cl_2...Ne_n (n = 2,3). The vibrational degree of freedom of the diatomic is treated quantum mechanically while all the other degrees of freedom are treated classically. A kinetic mechanism is proposed in order to interpret the dynamics in terms of the following elementary steps; vibrational predissociation (VP), intramolecular vibrational redistribution (IVR), and evaporative cooling (EC). The resulting lifetimes are in very good agreement with the experimental linewidth measurements of Janda and co-workers, and with the quantum mechanical reduced-dimension results of Le Quere and Gray on Cl_2...Ne_2. The final rotational state distributions agree very well with the experimental results and exhibit a quasistatistical behavior. The final vibrational distributions reproduce the main experimental features.