Activation of H2 by Gadolinium Cation (Gd+): Bond Energy of GdH+ and Mechanistic Insights from Guided Ion Beam and Theoretical Studies,The Journal of Physical Chemistry A

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Activation of H2 by Gadolinium Cation (Gd+): Bond Energy of GdH+ and Mechanistic Insights from Guided Ion Beam and Theoretical Studies
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-01-12 00:00:00 , DOI: 10.1021/acs.jpca.7b11471
Maria Demireva ₁ , P. B. Armentrout ₁

Affiliation

The energy-dependent reactions of the lanthanide gadolinium cation (Gd⁺) with H₂, D₂, and HD are investigated using guided ion beam tandem mass spectrometry. From analysis of the resulting endothermic product ion cross sections, the 0 K bond dissociation energy for GdH⁺ is measured to be 2.18 ± 0.07 eV. Theoretical calculations on GdH⁺ are performed for comparison with the experimental thermochemistry and generally appear to overestimate the experimental GdH⁺ bond dissociation energy. The branching ratio of the products in the HD reaction suggests that Gd⁺ reacts primarily via a statistical insertion mechanism to form the hydride product ion with contributions from direct mechanisms. Relaxed potential energy surfaces for GdH₂⁺ are computed and are consistent with the availability of both statistical and direct reaction pathways. The reactivity and hydride bond energy for Gd⁺ is compared with previous results for the group three metal cations, Sc⁺ and Y⁺, and the lanthanides, La⁺ and Lu⁺, and periodic trends are discussed.

中文翻译：

Ga阳离子（Gd ⁺）活化H ₂：GdH ^+的键能以及离子束和理论研究的机理性见解

使用引导离子束串联质谱法研究了镧系g阳离子（Gd ⁺）与H ₂，D ₂和HD的能量依赖反应。通过分析所得的吸热产物离子截面，测得GdH ⁺的0 K键解离能为2.18±0.07 eV。对GdH ⁺进行理论计算是为了与实验热化学进行比较，并且通常似乎高估了实验GdH ⁺键的解离能。HD反应中产物的支化比表明Gd ⁺反应主要是通过统计插入机制发生的，在直接机制的作用下形成了氢化物产物离子。计算出GdH ₂^+的弛豫势能面，并与统计和直接反应路径的可用性一致。将Gd ⁺的反应性和氢键能与之前的三个金属阳离子Sc ⁺和Y ⁺以及镧系元素La ⁺和Lu ^{+的结果进行了比较}，并讨论了其周期性趋势。

更新日期：2018-01-12

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