Non-resonant VV transfer in liquid Ar and in the gas phase at 85K

Abstract

Rate constants have been determined in the gas phase and in liquid Ar at 85 K under 1 atm pressure for non-resonant VV transfer in ten systems involving the isotopes of CO and N 2. For all cases the ratio k L/ k G is unity within the experimental errors. For the six cases using isotopes of CO which can be pumped optically, the mean value of k L/ k G is 1.01±0.05. We conclude that this is because in both phases, for the conditions employed, both the attractive and the repulsive portions of the interaction potentials must be used in calculating the pair distribution functions leading to very similar values in both phases. We anticipate that for all non-resonant VV and VT processes, k L measured near the gas-liquid coexistence region will equal k G within 10% provided that T* is small (⩽ 0.88 from these results), that the IBC hypothesis is obeyed and that the liquid imposes no constraint on the free rotation of the collision partners.