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Rotational distributions from photodissociations. I. Linear triatomic molecules

Journal Article · · J. Chem. Phys.; (United States)
DOI:https://doi.org/10.1063/1.437964· OSTI ID:6135832

The generalized Franck--Codon theory of the collinear dissociation of linear triatomic molecules is presented, including a proper description of the bending vibrations in the initial bound electronic state and of the rotational motions on both the initial and the final repulsive electronic surface. The nonseparable multidimensional bound--continuum Franck--Condon integrals are reduced to a rapidly convergent series of products of one dimensional integrals. Analytical expressions are derived for rotational and orbital angular momentum distributions of the products, for scalar coupling (as in predissociations), as well as parallel and perpendicular transitions (as in direct photodissociation). This fully quantum mechanical theory makes explicit the separate and interrelated roles played by angular momentum and energy conservation. The present work is applied in a separate paper to the photodissociation of ICN, and qualitative agrement with experiment is obtained.

Research Organization:
James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637
OSTI ID:
6135832
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 70:8; ISSN JCPSA
Country of Publication:
United States
Language:
English