Abstract
The theory of forward glory scattering is investigated for a state-to-state chemical reaction whose scattering amplitude can be written as a Legendre partial wave series. Legendre series occur in the exact quantum theory of reactive scattering when the initial and final helicity quantum numbers are zero, as well as in many approximate theories of chemical reactions. The starting point for the semiclassical theory is a two-dimensional integral representation for the scattering amplitude. A uniform semiclassical approximation is derived that is valid for angles both on, and off, the axial caustic associated with the glory. The derivation is the first application to a concrete problem in molecular physics of a method outlined by J. N. L. Connor and H. R. Mayne in 1979 for the uniform semiclassical evaluation of multidimensional integrals. The approach exploits the theory of singularities of differential mappings. The key step in the derivation is an exact one-to-one change of variables in the neighbourhood of the stationary phase points that locally reduce the two-dimensional phase of the integrand to a non-polynomial canonical form. The derivation complements a different semiclassical glory analysis reported in a companion paper.
Published Version
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