Abstract
Guided ion beam tandem mass spectrometry was used to study the reactions of the atomic lanthanide praseodymium cation (Pr+) with H2, D2, and HD as a function of collision energy. Modeling the kinetic-energy-dependent endothermic reactions to form PrH+ (PrD+) yields a 0 K bond dissociation energy (BDE) of 2.10 ± 0.05 eV for PrH+. Quantum chemical calculations were performed for PrH+ at the B3LYP, BHLYP, PBE0, and coupled-cluster with single, double, and perturbative triple levels of theory, and they overestimate the PrH+ experimental BDE by 0.06 -0.28 eV. The branching ratio of the PrH+ and PrD+ products in the HD reaction suggests that the reaction occurs via a direct reaction mechanism with short-lived intermediates. This is consistent with the theoretical calculations for the relaxed potential energy surfaces of PrH2 +, where no strongly bound dihydride intermediates were found. The reactivity and PrH+ BDE are compared with previous results for lanthanide metal cations (La+, Ce+, Sm+, Gd+, and Lu+). Periodic trends across the lanthanide series and insights into the role of the electronic configuration on metal-hydride bond strength are discussed.
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