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What is the Bond Dissociation Energy of the Vanadium Hydride Cation?
The Journal of Physical Chemistry A ( IF 2.9 ) Pub Date : 2020-06-05 , DOI: 10.1021/acs.jpca.0c04517
P B Armentrout 1 , Yih-Chung Chang 2 , Cheuk-Yiu Ng 2
Affiliation  

Recent electronic state-selected measurements of the reactions of atomic vanadium cations with D2 and CO2 are reanalyzed to properly account for the kinetic energy distribution of the reactant neutrals. The need for this is demonstrated in the present work by comparing the D2 data to that obtained previously in earlier experiments but unpublished. It is shown that the earlier data, which utilized a surface ionization source of V+, and the state-selected data for V+(a5D2) are essentially identical in the threshold regions where they overlap. Differences in the electronic state energies and kinetic energy distributions of V+ in the two experiments are very small and much smaller than the kinetic energy distribution of the neutral reactant, which is identical in both experiments. It is shown that properly accounting for the latter distribution alters the conclusions regarding the threshold energy for the endothermic formation of VD+ such that recent conclusions regarding the bond energy of VD+ are substantially altered and found to reproduce the original bond energy determination. Accounting for all experiments, a revised best value for D0(VH+) is 2.07 ± 0.09 eV [or D0(VD+) = 2.10 ± 0.09 eV]. This conclusion is validated by high-level ab initio calculations. Differences in the new and older data sets for the V+ + D2 reaction at higher energies (above the onset for dissociation of the product ion) are also discussed. The same methodology is then applied to recent studies on the state-selected V+ + CO2 reaction.

中文翻译:

氢化钒阳离子的键解离能是多少?

重新分析了原子钒阳离子与D 2和CO 2反应的最新电子状态选择测量结果,以适当考虑反应物中性物的动能分布。通过将D 2数据与先前在较早的实验中获得但未发表的数据进行比较,证明了对本工作的需求。结果表明,利用V +表面电离源的早期数据与V +a 5 D 2)的状态选择数据在重叠的阈值区域中基本相同。V +的电子态能和动能分布的差异在两个实验中,这非常小,远小于中性反应物的动能分布,这在两个实验中是相同的。结果表明,适当地占后者分布涂改关于用于吸热形成VD的阈值能量的结论+使得关于VD的键能最近结论+实质上改变,并且发现以再现原始键能测定。考虑到所有实验,D 0(VH +)的最佳修正值是2.07±0.09 eV [或D 0(VD +)= 2.10±0.09 eV]。该结论已通过高级从头算计算得到验证。还讨论了在更高能量下(高于产物离子离解的起点)V + + D 2反应的新数据和旧数据集的差异。然后将相同的方法应用于状态选择的V + + CO 2反应的最新研究。
更新日期:2020-07-02
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