Resonance Theory of Termolecular Recombination Kinetics: H+H+M→H2M

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Abstract
A theory is formulated for atomic recombination reactions which is based upon the identification of the set of transition complexes, X2i, as specific quasibound states or orbiting resonances. The conventional “energy-transfer mechanism” is assumed, since it has been justified under many experimental situations. Calculations, based on a modified distorted-wave approximation, demonstrate that the main contribution to the rate is that arising from rotational (rather than vibrational) transitions downwards from the quasibound to the bound states. Computations were carried out for the reaction H+H+M→H2+M for M = He, H2, and Ar making use of detailed ab initio knowledge of the spectrum of quasibound states and their wave-functions. Good agreement was found between the experimental rate constant and that calculated by the present resonance theory. The theory predicts a maximum in the rate in the temperature range between 65° and 100°K, attributed mainly to one particular quasibound state: υ = 14, j = 5. This suggests a promising region for further experimental investigation which could provide a critical check of the present theory.
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