Abstract
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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