A self-consistent eikonal treatment of diabatic rearrangement: Model H++H2 calculationsa)

Abstract

An eikonal treatment of nonadiabatic reactions, in which nuclear positions and momenta are self-consistently coupled to electronic transition amplitudes in a Hamiltonian formalism, is applied to H++H2 collisions where both electron transfer and nuclear rearrangement may occur. The approach is based on the diabatic electronic representation and uses potential energy surfaces and momentum couplings obtained within the method of diatomics-in-molecules. Equations of motion are obtained for hyperspherical coordinates in a model collinear treatment. Calculations carried out at collision energies 1 eV above the n=4 threshold of H2 illustrate reactive and nonreactive processes, electron transfer, and translational-vibrational energy transfer. Results for total electron transfer probabilities are compared with other calculations within the same model.