Experimental VV energy transfer from directly excited CO(v=2) and DCl(v=2)

Abstract
CO(v=2) and DCl(v=2) have been directly excited with a pulsed optical parametric oscillator. The total deactivation rate constants for CO(v=2) and DCl(v=2) in CO–DCl mixtures at 295 K are determined from the temporally and spectrally resolved infrared fluorescence. These rate constants are interpreted as single quantum VV exchange rates and have the magnitudes CO→CO 2.7±0.1; CO→DCl 3.7±0.3; DCl→CO 1.4±0.15; DCl→DC1(3.3±0.3)×10−12 cm3 s−1. For the data now available, it appears that for CO–DCl collisions energy transfer is faster for a given vibrational energy difference when the DCl quantum is larger.