Non-adiabatic Quantum Dynamics of the Dissociative Charge Transfer He⁺+H₂ → He+H+H

We present the non-adiabatic, conical-intersection quantum dynamics of the title collision where reactants and products are in the ground electronic states. Initial-state-resolved reaction probabilities, total integral cross sections, and rate constants of two H₂ vibrational states, v ₀ = 0 and 1, in the ground rotational state (j ₀ = 0) are obtained at collision energies E _coll ≤ 3 eV. We employ the lowest two excited diabatic electronic states of $$ and their electronic coupling, a coupled-channel time-dependent real wavepacket method, and a flux analysis. Both probabilities and cross sections present a few groups of resonances at low E _coll, whose amplitudes decrease with the energy, due to an ion-induced dipole interaction in the entrance channel. At higher E _coll, reaction probabilities and cross sections increase monotonically up to 3 eV, remaining however quite small. When H₂ is in the v ₀ = 1 state, the reactivity increases by ~2 orders of magnitude at the lowest energies and by ~1 order at the highest ones. Initial-state resolved rate constants at room temperature are equal to 1.74 × 10^-14 and to 1.98 × 10^-12 cm³s^-1 at v ₀ = 0 and 1, respectively. Test calculations for H₂ at j ₀ = 1 show that the probabilities can be enhanced by a factor of ~1/3, that is ortho-H₂ seems ~4 times more reactive than para-H₂.