Reactions of the atomic lanthanide cerium cation (Ce⁺) with H₂, D₂, and HD were studied by using guided ion beam tandem mass spectrometry. Analysis of the kinetic-energy-dependent endothermic reactions to form CeH⁺ (CeD⁺) led to a 0 K bond dissociation energy (BDE) for CeH⁺ of 2.19 ± 0.09 eV. Theoretical calculations for CeH⁺ were performed at the B3LYP, BHLYP, and PBE0 levels of theory and overestimate the experimental BDE. In contrast, extrapolation to the complete basis set limit using coupled-cluster with single, double, and perturbative triple excitations, CCSD(T), gave a value (2.33 eV) in reasonable agreement with the experimental BDE. The branching ratio of the CeH⁺ and CeD⁺ products in the HD reaction suggests that the reaction occurs via a statistical mechanism involving a long-lived intermediate. Relaxed potential energy surfaces for CeH₂⁺ were computed and are consistent with the availability of such an intermediate, but the crossing point between quartet and doublet surfaces helps explain the inefficiency of the association reaction observed in the literature. The reactivity and CeH⁺ BDE are compared with previous results for group 4 transition metal cations (Ti⁺, Zr⁺, and Hf⁺), other lanthanides (La⁺, Sm⁺, Gd⁺, and Lu⁺), and the isovalent actinide Th⁺. Periodic trends and insight into the role of the electronic configuration on metal–hydride bond strength are discussed.

中文翻译：

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铈与H ₂，D ₂和HD的阳离子（Ce ⁺）反应：CeH ⁺键能以及来自离子导束和理论研究的机理研究

利用导向离子束串联质谱研究了镧系元素铈阳离子（Ce ⁺）与H ₂，D ₂和HD的反应。的动能相关的吸热反应的分析，以形成CEH ⁺（CED ⁺）导致了0 K时键离解能（BDE），用于CEH ⁺ 2.19±0.09电子伏特。CeH ^+的理论计算在理论上以B3LYP，BHLYP和PBE0的水平进行，并高估了实验性BDE。相比之下，使用具有单，双和微扰三重激发的耦合簇CCSD（T）外推到完整基集极限，得出的值（2.33 eV）与实验BDE合理一致。HD反应中CeH ⁺和CeD ⁺产物的支化比表明，该反应是通过涉及长寿命中间体的统计机制发生的。CeH ₂ ^+的弛豫势能面的计算，并与这种中间体的可用性一致，但四重奏和双峰表面之间的交叉点有助于解释文献中观察到的缔合反应的低效率。将反应性和CeH ⁺ BDE与第4组过渡金属阳离子（Ti ⁺，Zr ⁺和Hf ⁺），其他镧系元素（La ⁺，Sm ⁺，Gd ⁺和Lu ⁺）以及等价act系元素的先前结果进行比较。日⁺。讨论了周期性趋势以及对电子构型对金属氢化物键强度的作用的认识。