Understanding the effect of vibrational excitation in reaction dynamics: the Ne + H2~+(v = 0-17,j = 1) → NeH~+ + H, Ne + H~+ + H proton transfer and dissociation cross sections

摘要

The dependence of the cross section (σ) of the Ne + H2~+→ NeH~+ + H proton transfer reaction on the vibrational excitation of H2~+, v = 0-17 and; = 1, was analyzed in detail at the collision energies (E_(col)) of 0.7 and 1.7 eV, using the quasi-classical trajectory (QCT) method and the PHHJ3 and LZHH potential energy surfaces (PESs), taking advantage of the rich experimental data available for this reaction as a function of H2~+(v). The efficiency of vibrational excitation to promote the reaction was investigated from the analysis of the u(QCT) vs. v dependence in terms of the average reaction probability, maximum impact parameter, regions of the (late barrier) PES explored, and taking into account the Ne + H2~+→ Ne + H~+ + H dissociative channel, which plays a dominant role at high enough total energies. Although the earlier PHHJ3 PES performs rather well, the LZHH PES QCT results show a better agreement with the experiment. On the other hand, some artifacts were found in recently reported QCT calculations (unphysical oscillations in o-(QCT) as a function of v), and the present study shows that special care is needed when carrying out QCT calculations involving highly excited vibrational states.