Intramolecular Vibration-to-Vibration Energy Transfer in Carbon Dioxide

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.