Rotational and translational effects in collisions of electronically excited diatomic hydrides
Collisional quenching and vibrational energy proceed competitively with rotational energy transfer for several excited states of the diatomic radicals OH, NH, and CH. This occurs for a wide variety of molecular collision partners. This phenomenon permits the examination of the influence of rotational motion on the collision dynamics of these theoretically tractable species. Measurements can also be made as a function of temperature, i.e., collision velocity. In OH (sup 2 sigma +), both vibrational transfer and quenching are found to decrease with an increase in rotational level, while quenching decreases with increasing temperature. This behavior indicates that for OH, anisotropic attractive forces govern the entrance channel dynamics for these collisions. The quenching of NH (sup 3 pi sub i) by many (although not all) collision partners also decreases with increasing rotational and translational energy, and NH (sup 1 pi) behaves much like OH (sup 2 sigma +). However, the quenching of CH (sup 2 delta) appears to decrease with increasing rotation but increases with increasing temperature, suggesting in this case anisotropic forces involving a barrier or repulsive wall. Such similarities and differences should furnish useful comparisons with both simple and detailed theoretical pictures of the appropriate collision dynamics.