Comment on the rotational state dependence of indirect photodissociation of a polyatomic molecule.
The rotational state dependence of indirect photodissociation has been examined in the light of some recent developments in the theory of radiationless transitions in rotating molecules. A simple argument based on projection operators leads to the prediction of sequential kinetics from an initial singlet state through an intermediate triplet bound state and on to a final dissociative state. The results indicate that as long as the geometry of the molecule in the triplet state is not very different from that of the singlet state, only a very small rotational dependence will show up in the singlet state radiationless lifetime, in spite of the fact that the overall dissociation constitutes a large geometry change.
The Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637.
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Novak
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Rice