The vibrational fluorescence quenching method has been used to measure the temperature dependence of the CO(v = 1) collisional transfer rates with CH4, CF4, and SF6 between 100 and 350 K. The V–V energy transfer rates for the CO–CF4 system were found to be much faster than the CO–CH4 system even though the fundamental band center energy mismatch is greater for CO–CF4. Also, the CO–CF4 system exhibited an inverse temperature dependence, indicating near resonant processes possibly arising from a multiple quantum exchange.
Vibration to vibration energy transfer rates for the CO–CS2 system have been experimentally determined between 198 and 371 K. At 300 K, the V-V rate was found to be 1.36×104 torr−1·sec−1, orders of magnitude faster than would be expected from a system having a fundamental band center energy mismatch of 608 cm−1, if transfers to overtone and combination bands are neglected. Experimental and theoretical evidence are presented which indicate that the observed rates arise from a multiquantum process. The implications for CS2 and CS2–O2(CO) laser systems are discussed.
The present study reports the measurement of the V-V energy transfer rates for the CO*-COS system in the temperature range of 195 to 370OK. The measured rates exhibit a slight inverse temperature dependence. The experimental results are compared to prediction based on a model of long-range dipole-dipole interactions between colliding molecules. The effect of single quantum rotational transitions is compared to that of multiquantum rotational transitions.
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