The bond energy of UN+: Guided ion beam studies of the reactions of U+ with N2 and NO

Bubas, Amanda R.; Kafle, Arjun; Stevenson, Brandon C.; Armentrout, Peter B.

doi:10.1063/5.0204090

Title: The bond energy of UN⁺: Guided ion beam studies of the reactions of U⁺ with N₂ and NO

Journal Article · 21 April 2024 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0204090 · OSTI ID:2350842

Bubas, Amanda R. ^[1];

^[2]; Stevenson, Brandon C. ^[2];

^[2]

Univ. of Utah, Salt Lake City, UT (United States); Department of Chemistry, University of Utah
Univ. of Utah, Salt Lake City, UT (United States)

In this work, a guided ion beam tandem mass spectrometer was used to study the reactions of U⁺ with N₂ and NO. Reaction cross sections were measured over a wide range of energy for both systems. In each reaction, UN⁺ is formed by an endothermic process, thereby enabling the direct measurement of the threshold energy and determination of the UN⁺ bond dissociation energy. For the reaction of U⁺ + N₂, a threshold energy (E₀) of 4.02 ± 0.11 eV was measured, leading to D₀ (UN⁺) = 5.73 ± 0.11 eV. The reaction of U⁺ + NO yields UO⁺ through an exothermic, barrierless process that proceeds with 94 ± 23% efficiency at the lowest energy. Analysis of the endothermic UN⁺ cross section in this reaction provides E₀ = 0.72 ± 0.11 eV and, therefore, D₀ (UN⁺) = 5.78 ± 0.11 eV. Averaging the values obtained from both reactions, we report D₀ (UN⁺) = 5.76 ± 0.13 eV as our best value (uncertainty of two standard deviations). Combined with precise literature values for the ionization energies of U and UN, we also derive D₀ (UN) = 5.86 ± 0.13 eV. Both bond dissociation energies agree well with high-level theoretical treatments in the literature. The formation of UN⁺ in reaction of U⁺ with NO also exhibits a considerable increase in reaction probability above ~3 eV. Theory suggests that this may be consistent with the formation of UN⁺ in excited quintet spin states, which we hypothesize are dynamically favored because the number of 5f electrons in reactants and products is conserved.

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Research Organization:: Univ. of Utah, Salt Lake City, UT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012249

OSTI ID:: 2350842

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 160; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
coupled-cluster methods
ions and properties
thermochemistry
threshold energy
actinides
guided ion beam mass spectrometry
chemical bonding
chemical reaction cross sections

Title: The bond energy of UN+: Guided ion beam studies of the reactions of U+ with N2 and NO

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Title: The bond energy of UN⁺: Guided ion beam studies of the reactions of U⁺ with N₂ and NO