Non-adiabatic Quantum Dynamics of the Dissociative Charge Transfer He+H → 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 H vibrational states, = 0 and 1, in the ground rotational state ( = 0) are obtained at collision energies ≤ 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 , whose amplitudes decrease with the energy, due to an ion-induced dipole interaction in the entrance channel. At higher , reaction probabilities and cross sections increase monotonically up to 3 eV, remaining however quite small. When H is in the = 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 and to 1.98 × 10 cms at = 0 and 1, respectively. Test calculations for H at = 1 show that the probabilities can be enhanced by a factor of ~1/3, that is H seems ~4 times more reactive than H.