Theoretical studies of tunneling processes in three-body exchange reactions of van der Waals rare gas dimers

Abstract

Rare gas atom–diatom collisions of Ar+Ar2, Xe+Ar2, Kr+Xe2, Kr+Ne2, and Kr+NeAr have been investigated to determine the importance of tunneling processes in exchange and dissociation reactions involving van der Waals molecules. Reaction cross sections, angular distributions, and product-energy distributions have been computed using Monte Carlo quasiclassical trajectories. The effect of tunneling through the rotational barrier upon these quantities has been computed using WKB methods. The results show that metastable diatomic products with energies above the classical dissociation limit, but below the rotational barrier, play a significant role in the dynamics of both exchange and dissociation reactions. Lifetime distributions of such metastable dimers illustrate their importance in crossed molecular beam studies of rare gas systems. The WKB calculations indicate that a significant, and possibly measurable, number of the metastables dissociate by tunneling before they would reach the detector in a molecular beam experiment. Close agreement has been found between these calculations and statistical state-counting calculations of metastable product dimer lifetimes. Experiments are suggested that might permit the direct observation of tunneling in these systems.