Journal of Chemical Physics, Vol.104, No.1, 139-147, 1996
Vibrational Frequency-Shift of H-2 in Rare-Gas Clusters and Solutions - Comparison of Semiclassical Theory and Experiment
A recently developed semi-classical statistical mechanical formulation [de Souza et al., J. Chem. Phys. 99, 9954 (1993)] is combined with accurate H-2-rare gas potentials [Le Roy and Hutson, J. Chem. Phys. 86, 837 (1987)] to predict H-2 vibrational frequency shifts in rare gas clusters and low density solutions. The results are compared with available experimental measurements as well as with predictions derived assuming a Lennard-Jones (LJ) atom-atom potential. The Le Roy-Hutson potential has a minimum cluster energy and maximum H-2 bond softening in the linear atom-diatom geometry, in contrast to the T geometry predicted using the LJ potential. The Le Roy-Hutson potential also yields better agreement with experimental temperature and density dependent H-2 frequency shifts. A classical approximation to the ground state frequency of H-2-rare gas clusters is suggested which relates the probability density of the cluster configuration to the classical Boltzmann distribution at a temperature equal to the cluster zero point energy.
Keywords:POTENTIAL-ENERGY SURFACES;B-STATE;DISSOCIATION;MOLECULES;COMPLEX;SOLVENT;LIQUIDS;FORCES;FLUIDS;AR