Three-dimensional natural coordinate asymmetric top theory of reactions: Application to H + H2

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Abstract
A particular partitioning of the Hamiltonian in natural collision coordinates is shown to lead to the use of hindered asymmetric top basis functions to represent all rotational motion (triangle tumbling plus internal bending) during reaction. These functions (along with perturbed Morse oscillator functions) are used as an adiabatic basis for expansion of the scattering wavefunction. The theory is discussed for both one and two reaction path potentials. The close coupled equations for the translational wavefunctions are then solved for the H + H2 reaction at total angular momentum J = 0. Wavefunction bifurcation and matching at the reactant–product boundary surface is considered in detail. Finally, numerical results (reaction probabilities, probability conservation, detailed balance, energy dependence of reactive S‐matrix elements, probability density, wavefunction real part, and flux) are presented and comparisons are made with other quantum mechanical, semiclassical, and statistical reaction studies.

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