Vibration-vibration equilibration in laser excited CH3F and CH3F-X mixtures

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Abstract
The infrared fluorescence risetime of the ν1,ν4 C–H stretching modes of CH3F has been measured in CH3F‐rare‐gas mixtures after pumping of the ν3 C–F stretching modes with a Q‐switched CO2 laser. The pressure‐dependent rate of rise was found to be 122 ± 25 msec−1 · torr−1 in pure CH3F. The effect of rare gases on this rate process was also studied and found to be consistent with a vibration‐vibration filling mechanism for ν1,ν4 involving a small amount of energy transfer (≤ 75 cm−1) into the translational/rotational degrees of freedom.