Non-adiabatic Quantum Dynamics of the Dissociative Charge Transfer He(+)+H(2) → He+H+H()

非绝热量子动力学解离电荷转移 He(+)+H(2) → He+H+H()

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Abstract

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(2) 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 HeH2+ 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 H(2) 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) cm(3)s(-1) at v (0) = 0 and 1, respectively. Test calculations for H(2) at j (0) = 1 show that the probabilities can be enhanced by a factor of ~1/3, that is ortho-H(2) seems ~4 times more reactive than para-H(2).

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