Near- and non-resonant (VV) energy transfer between molecules dissolved in liquid krypton: a comparison with liquid argon

Abstract

Rate constants have been measured for the vibrational deactivation of the isotopes of CO by the collision partners, O 2, CH 4, CH 3D, CD 3H and CD 4 under irreversible conditions both in liquid Kr solution at 118 K and in the gas phase at the same temperature in the presence of an inert buffer gas. For the five non-resonant processes with energy mismatch > 150 cm −1 the ratio of the rate constants k L/ k G = 1.39 ± 0.07. This result is very important since all of the systems studied previously in liquid Ar at 85 K gave the result k L/ k G = 1.03 ± 0.05. The change in the ratio of k L/ k G between liquid argon and liquid krypton may be due either to the change in solvent, or the change in temperature. The values of k L/ k G for the five near-resonant systems vary with energy mismatch in a manner very similar to those for near-resonant vibration-vibration exchange processes measured in liquid Ar solution at 85 K. These can be accounted for by the influence of the solvent on the energy transfer process and represent a breakdown of the isolated binary collision hypothesis.