The temperature dependence of fast vibrational energy transfer processes in methyl fluoride
The temperature dependencies of two fast vibrational energy transfer processes in methyl fluoride (CH3F) have been measured between 120K and 400 K by means of time-resolved millimetre/submillimetre-infrared double resonance spectroscopy. The first of these processes, a resonant vibrational swapping process between the ground vibrational state and the v3 = 1 (V3) vibrational state, effectively transfers population between states of A and E symmetry. A rapid increase in cross section with decreasing temperature was observed for this process, a result in excellent quantitative agreement with semi- classical theory of near resonant vibrational collisions. The second process, which transfers population between the v3 and v6 = 1 (v6) vibrational states, was found experimentally to have a much weaker temperature dependence. From this result and from additional experimental observations of symmetry type-sensitive energy transfer into v6, the energy transfer between v3and v6 was demonstrated to result from a ‘direct’ vibrational energy transfer rather than from an ‘indirect’ vibrational swap process. © 1993 Taylor and Francis Ltd.
Everitt, HO; de Lucia, FC
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