The endothermic proton transfer reaction, H2+(v+,N+=1)+Ne→NeH++H(ΔH=0.54 eV), is investigated over a broad range of reactant vibrational energies using the pulsed-field ionization–photoelectron–secondary ion coincidence (PFI–PESICO) scheme. For the lowest vibrational levels, v+=0 and 1, a detailed translational energy dependence is also presented using a continuous approach for preparing reactant ions with monochromatic VUV. Sharp threshold onsets are observed, suggesting the importance of long-lived intermediates or resonances. At a translational energy, ET=0.7 eV, absolute state-selected reaction cross sections are measured for all reactant vibrational levels v+=0–17. For levels v+=0–6, the cross sections grow rapidly with vibrational quantum, above which the cross sections saturate at a value of ∼13±4 Å2. At levels v+>13, the cross sections decline, probably due to competition with the dissociation channel. At a translational energy, ET=1.7 eV, absolute state-selected reaction cross sections are measured for reactant vibrational levels spanning the range between v+=0 and 14. Cross section growth is observed from v+=0–7, above which the cross sections no longer exhibit a steady trend. At ET=4.5 eV, cross sections are reported for vibrational levels covering the range between v+=0 and 12. The cross sections are substantially lower at this high translational energy, however, they still exhibit a substantial vibrational enhancement below v+=8. The present measurements are compared with quasiclassical trajectory (QCT) calculations. The comparison can be categorized by three distinct total energy (Etot=ET+Evib) regimes. For Etot<1 eV, the experimental cross sections exceed the QCT results, consistent with important quantum effects at low energies. For 1<Etot<3 eV, excellent agreement is observed between the PFI–PESICO cross sections and the QCT calculations. At total energies exceeding 3 eV, the experimental results are generally higher, probably because QCT overpredicts competition from the dissociation channel.
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Zhang et al. (2003) studied this question.
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