Guided ion beam tandem mass spectrometry (GIBMS) was used to measure the kinetic energy dependent product ion cross sections for reactions of the lanthanide metal praseodymium cation (Pr⁺) with O₂, CO₂, and CO and reactions of PrO⁺ with CO, O₂, and Xe. PrO⁺ is formed through barrierless exothermic processes when the atomic metal cation reacts with O₂ and CO₂, whereas all other reactions are observed to be endothermic. Analyses of the kinetic energy dependences of these cross sections yield 0 K bond dissociation energies (BDEs) for PrO⁺, PrC⁺, PrCO⁺, and PrO₂⁺. The 0 K BDE for PrO⁺ is determined to be 7.62 ± 0.09 eV from the weighted average of five independent thresholds. This value is combined with the well-established ionization energy (IE) of Pr to indicate an exothermicity of the chemi-ionization reaction, Pr + O → PrO⁺ + e⁻, of 2.15 ± 0.09 eV. Additionally, BDEs of Pr⁺–C, OPr⁺–O, and Pr⁺–CO are determined to be 2.97 ± 0.10. 2.47 ± 0.11, and 0.31 ± 0.07 eV. Theoretical Pr⁺–O, Pr⁺–C, OPr⁺–O, and Pr⁺–CO BDEs are calculated for comparison with experimental values. The Pr⁺–O BDE is underestimated at the B3LYP and PBE0 level of theory but better agreement is obtained using the coupled-cluster with single, double, and perturbative triple excitations, CCSD(T), level. Density functional theory approaches yield better agreement for the BDEs of Pr⁺–C, OPr⁺–O, and Pr⁺–CO.

中文翻译：

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Pr + O→PrO + + e-化学电离反应焓和oxide氧化物，碳化物，二氧化物和羰基阳离子键能的评估

引导离子束串联质谱（GIBMS）用于测量镧系元素金属ody阳离子（Pr ⁺）与O ₂，CO ₂和CO的反应以及PrO ⁺与CO的反应的动能依赖性产物离子截面， O ₂和Xe。当原子金属阳离子与O ₂和CO ₂反应时，PrO ⁺是通过无障碍放热过程形成的，而所有其他反应都被认为是吸热的。这些横截面的动能依赖性的分析收率为Pro 0 K时键离解能（二苯醚）⁺，PRC ⁺，濮耐⁺和PrO ₂ ⁺。从五个独立阈值的加权平均值确定PrO ⁺的0 K BDE为7.62±0.09 eV。这个值与成熟的电离能量Pr的（IE）结合，以指示化学-电离反应的放热性，镨+ O→了PrO ⁺ + E ^- 2.15±0.09电子伏特。另外，确定Pr ⁺ –C，OPr ⁺ –O和Pr ⁺ –CO的BDE为2.97±0.10。2.47±0.11和0.31±0.07 eV。计算理论上的Pr ⁺ –O，Pr ⁺ –C，OPr ⁺ –O和Pr ⁺ –CO BDE与实验值进行比较。Pr ⁺-O BDE在理论上的B3LYP和PBE0水平上被低估，但使用具有单，双和扰动三重激发CCSD（T）水平的耦合簇，可以获得更好的一致性。密度泛函理论方法对于Pr ⁺ –C，OPr ⁺ –O和Pr ⁺ –CO的BDE具有更好的一致性。