Summary: Orbital alignment during cage-exit of open-shell photofragments: F in solid
Ar and Kr
K. S. Kizer and V. A. Apkarian
Department of Chemistry, University of California, Irvine, California 92717
Received 12 April 1995; accepted 19 June 1995
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 F2 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 2 smaller than
the experimental values. © 1995 American Institute of Physics.
I. INTRODUCTION
The many-body dynamics of open-shell fragments, with
orbital degeneracy 1 1 , cannot be described by a single
potential-energy surface. In effect, the Born­Oppenheimer
separation between electronic and nuclear degrees of free-
dom breaks down, and it is necessary to consider the coupled
electronic nuclear motions in describing processes relevant
to chemistry. The cage-exit dynamics of an F atom in rare

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

Collections: Chemistry