Angular momentum analysis of rotational transfer of superthermal relative velocity distributions

An angular momentum (AM) theory is developed to calculate the relative populations of final rotational states after collision between a diatomic molecule and an atom having a narrow, superthermal velocity distribution as produced by, e.g. photolysis of a precursor species. Probability densities are derived from semiclassical expressions for energy and angular momentum assuming the classically impulsive limit with the repulsive wall modelled by a hard ellipsoid. The treatment given is general and therefore applies to molecules in which the centre-of-mass does not coincide with the centre of the potential coordinates. A transfer function for RT is derived and applied to the H + CO system. Analysis of the data allows the anisotropy to be extracted which is in good agreement with an ab initio potential surface. The method described allows one to rapidly assess the contributions from the elliptical core of the potential and from other features of the potential, and would permit more sophisticated representations of the topology to be incorporated.