Evaluation of the Pr + O → PrO+ + e− chemi-ionization reaction enthalpy and praseodymium oxide, carbide, dioxide, and carbonyl cation bond energies

文献情報

出版日 2021-01-18

DOI 10.1039/D0CP06252A

インパクトファクター 3.676

著者

Maryam Ghiassee, Brandon C. Stevenson, P. B. Armentrout

原文を見る

要旨

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.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.