Intramolecular Vibration-to-Vibration Energy Transfer in Carbon Dioxide

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Abstract
We have used a vibrational fluorescence technique to study the deactivation of the asymmetric stretching vibration (00°1) of CO2 by intramolecular vibration‐to‐vibration energy transfer during CO2—rare‐gas collisions. The efficiency for deactivation has only a slight dependence on mass, with a peak corresponding to resonance between the duration of the collision and the frequency difference between the vibrational levels involved. We have been able to obtain order‐of‐magnitude agreement between observed and theoretical transition probabilities only when the mixing of vibrational states of CO2 by Coriolis coupling and anharmonicity is considered.