ORBITAL ALIGNMENT DURING CAGE-EXIT OF OPEN-SHELL PHOTOFRAGMENTS - F IN SOLID AR AND KR

The statistical theory for sudden cage-exit [J. Zoval and V. A. Apkarian, J. Phys. Chem, 98; 7945 (1994)] is extended to orbitally degenerate photofragments, specifically treating the case of F atoms in solid Ar and Kr. It is shown that the experimental energy-dependent, quantum yields of photodissociation of F-2 are only compatible with the p hole on the F atom being completely aligned parallel to the cage wall during the sudden exit. Although relative quantum;yields and energy thresholds are well predicted, the calculated absolute quantum yields are a factor of similar to 2 smaller than the experimental values. (C) 1995 American Institute of Physics.