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Laser fluorescence study of vibrational energy transfer in CH3Cl

A laser induced infrared fluorescence technique has been used to measure both vibration to vibration and vibration to translation/rotation energy transfer rates in CH3Cl. The V-T/R rates were measured using H2, D2, CH4, and rare gases as collision partners. Qualitative comparison of these data with...

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Bibliographic Details
Published in:The Journal of chemical physics 1973-01, Vol.58 (7), p.2684-2689
Main Authors: Knudtson, J. Thomas, Flynn, George
Format: Article
Language:English
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Summary:A laser induced infrared fluorescence technique has been used to measure both vibration to vibration and vibration to translation/rotation energy transfer rates in CH3Cl. The V-T/R rates were measured using H2, D2, CH4, and rare gases as collision partners. Qualitative comparison of these data with V → T and V → R theories indicates that the V → T mechanism dominates for collisions with small reduced masses while the V → R mechanism dominates for collisions with large reduced masses. The V–V rate equilibrating the ν6 and ν3 modes was measured as a function of CH3Cl pressure and was found to be 76 msec−1· torr−1. A lower limit was also obtained for the rate of V–V energy transfer from states near 1000 cm−1 to high lying states near 3000 cm−1.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1679568