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Semiclassical approximations for low-energy inelastic scattering

Journal Article · · J. Chem. Phys.; (United States)
DOI:https://doi.org/10.1063/1.436439· OSTI ID:6616703

Several semiclassical methods are developed to treat low-energy vibrationally and rotationally inelastic scattering. The quantal close coupling (CC) equations are approximated by treating the orbital angular momentum in a classical limit. This removes l from the coupled equations and introduces a dependence in the potential on the classical orbital angle. Unlike the coupled states (CS) approximation, l is not frozen. Next, the rotational motion is treated in the sudden approximation. For vibrationally inelastic scattering, this yields an approximation which involves the solution of N coupled differential equations for N vibrational states. For the pure rotational case, the theory reduces to a sudden approximation superior to the current alternatives. Unlike the traditional approach, it is not a perturbation theory based on an elastic trajectory. Unlike the infinite order sudden approximation (IOS), it converges properly at large impact parameters. Indeed, the IOS is obtained as a special case by freezing the orbital motion. A fast numerical procedure is derived for evaluating the matrices occurring in the sudden approximation.

Research Organization:
Department of Chemistry, Yale University, New Haven, Connecticut 06520
OSTI ID:
6616703
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 69:10; ISSN JCPSA
Country of Publication:
United States
Language:
English