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In order to investigate the effect of the solvent on nonresonant (VV) processes, rate constants have been measured for the deactivation of N2(v=1) and CO(v=1) in liquid N2/Ar mixtures at 85 K. The systems studied are relaxation of 14N2, 12C16O, and 13C16O by both O2 and CH4. Measurements were taken in liquid Ar, liquid N2, and in solvent mixtures. The rate constants in liquid Ar solution equal those in the gas phase at the same temperature. The rate constants fall nonlinearly with the addition of N2 to the solvent. The decrease on changing the solvent from liquid Ar to liquid N2 is 30% for the deactivation of N2(v=1) and 10% for CO(v=1). These results would not be predicted by current formulations of the isolated binary collision (IBC) hypothesis and suggest that one or more N2 molecules in the shell of solvent molecule surrounding vibrationally excited N2 or CO perturb the energy transfer process.

Rate constants are presented for (VV) energy transfer between CO(ν=1) and CO2(0001) in the gas phase down to 115 K and in liquid Kr solution at 118 and 130 K. Four isotopically substituted systems were investigated for which the energy mismatches varied between 104 and 306 cm−1. The gas and liquid phase data show several systematic effects with changing energy mismatch. In particular it was found that the ratio of the liquid and gas phase rate constants at the same temperature, kL/kG, increased with decreasing energy mismatch. This is not predicted by current theories of liquid phase energy transfer and is in contrast to previous work using liquid Kr as the solvent.

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