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Title: A guided ion beam investigation of UO2+ thermodynamics and f orbital participation: Reactions of U+ + CO2, UO+ + O2, and UO+ + CO

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0183836 · OSTI ID:2263368
 [1];  [2]; ORCiD logo [2]
  1. University of Utah, Salt Lake City, UT (United States); Department of Chemistry, University of Utah
  2. University of Utah, Salt Lake City, UT (United States)
+ Show Author Affiliations

A guided ion beam tandem mass spectrometer was employed to study the reactions of U+ + CO2, UO+ + O2, and the reverse of the former, UO+ + CO. Reaction cross sections as a function of kinetic energy over about a three order of magnitude range were studied for all systems. The reaction of U+ + CO2 proceeds to form UO+ + CO with an efficiency of 118% ± 24% as well as generating UO2+ + C and UCO+ + O. The reaction of UO+ + O2 forms UO2+ in an exothermic, barrierless process and also results in the collision-induced dissociation of UO+ to yield U+. In the UO+ + CO reaction, the formation of UO2+ in an endothermic process is the dominant reaction, but minor products of UCO+ + O and U+ + (O + CO) are also observed. Analysis of the kinetic energy dependences observed provides the bond energies, D0(U+–O) = 7.98 ± 0.22 and 8.05 ± 0.14 eV, D0(U+–CO) = 0.73 ± 0.13 eV, and D0(OU+–O) = 7.56 ± 0.12 eV. The values obtained for D0(U+–O) and D0(OU+–O) agree well with the previously reported literature values. To our knowledge, this is the first experimental measurement of D0(U+–CO). Furthermore, an analysis of the oxide bond energies shows that participation of 5f orbitals leads to a substantial increase in the thermodynamic stability of UO2+ relative to ThO2+ and especially transition metal dioxide cations.

Research Organization:
University of Utah, Salt Lake City, UT (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
SC0012249
OSTI ID:
2263368
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 159; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (60)

Kinetic energy dependence of Al + +O 2 →AlO + +O journal February 1986
Reactions of U+ and UO+ with O2, CO, CO2, COS, CS2 and D2O journal August 1980
Reactions of fourth‐period metal ions (Ca + −Zn + ) with O 2 : Metal‐oxide ion bond energies journal August 1990
Lanthanides as Catalysts: Guided Ion Beam and Theoretical Studies of Sm + + COS journal January 2018
The bond energy of ReO + : Guided ion-beam and theoretical studies of the reaction of Re + ( 7 S) with O 2 journal August 2013
A comparative theoretical study of bonding in UO2++,UO2+,UO2,UO2−, OUCO, O2U(CO)2 and UO2CO3 journal July 2002
An ab Initio Theoretical Study of the Electronic Structure of UO 2 + and [UO 2 (CO 3 ) 3 ] 5− journal February 2009
Reactions of Fe+, Co+, and Ni+ with Silane. Electronic State Effects, Comparison to Reactions with Methane, and M+-SiHx (x = 0-3) Bond Energies journal January 1995
Kinetic energy dependence of ion–molecule reactions: guided ion beams and threshold measurements journal December 2000
The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides journal March 2014
Collision-induced dissociation of Nb+n (n = 2 − 11): bond energies and dissociation pathways journal December 1990
Why uranyl ion(2+) is linear and isoelectronic thorium dioxide is bent journal October 1981
Spectroscopy of the UO2+ cation and the delayed ionization of UO2 journal February 2008
Gadolinium cation (Gd + ) reaction with O 2 : Potential energy surface mapped experimentally and with theory journal May 2017
Gas-phase thermochemistry of the group 3 dioxides: ScO2, YO2 and LaO2 journal March 1992
Guided Ion Beam Studies of the Dy + O → DyO+ + e– Chemi-ionization Reaction Thermochemistry and Dysprosium Oxide, Carbide, Sulfide, Dioxide, and Sulfoxide Cation Bond Energies journal December 2022
Radiationless transitions in a new light journal October 1983
Scintillation Type Mass Spectrometer Ion Detector journal March 1960
Translational energy dependence of O+(4S) + H2(D2, HD) → OH+(OD+) + H(D) from thermal energies to 30 eV c.m. journal December 1987
Theory of translationally driven reactions journal April 1979
Reactions of pulsed‐laser evaporated uranium atoms with molecular oxygen: Infrared spectra of UO, UO 2 , UO 3 , UO 2 + , UO 2 2+ , and UO 3 –O 2 in solid argon journal March 1993
Collision‐induced dissociation of Fe + n ( n =2–10) with Xe: Ionic and neutral iron binding energies journal May 1989
Reliable Potential Energy Surfaces for the Reactions of H 2 O with ThO 2 , PaO 2 + , UO 2 2+ , and UO 2 + journal November 2015
Reactions of Y + , Zr + , Nb + , and Mo + with H 2 , HD, and D 2 journal January 1996
Evaluation of the exothermicity of the chemi-ionization reaction Nd + O → NdO + + e − and neodymium oxide, carbide, dioxide, and carbonyl cation bond energies journal April 2019
Activation of CO2 by Gadolinium Cation (Gd+): Energetics and Mechanism from Experiment and Theory journal November 2017
Kinetic-energy dependence of competitive spin-allowed and spin-forbidden reactions: V++CS2 journal April 1999
Bond Energies of UO+ and UC+: Guided Ion Beam and Quantum Chemical Studies of the Reactions of Uranium Cation with O2 and CO journal April 2023
Charge-transfer dynamics in ion–polyatomic molecule collisions: X++H2O (X=N,Kr) luminescence study journal December 1995
Guided Ion Beam Studies of the Reactions of Group 3 Metal Ions (Sc+, Y+, La+, and Lu+) with Silane. Electronic State Effects, Comparison to Reactions with Methane, and M+-SiHx (x = 0-3) Bond Energies journal April 1995
Guided ion beam study of collision-induced dissociation dynamics: integral and differential cross sections journal July 2001
Thermochemical Data for Gaseous Monoxides journal October 1983
Collision-induced dissociation of UO+ and UO+2 journal August 1980
Potential energy surface for the reaction Sm + + CO 2 → SmO + + CO: guided ion beam and theoretical studies journal January 2017
Electronic spectroscopy and ionization potential of UO2 in the gas phase journal March 2004
Gadolinium (Gd) Oxide, Carbide, and Carbonyl Cation Bond Energies and Evaluation of the Gd + O → GdO + + e – Chemi-Ionization Reaction Enthalpy journal October 2016
Holmium (Ho) oxide, carbide, and dioxide cation bond energies and evaluation of the Ho + O → HoO + + e − chemi-ionization reaction enthalpy journal September 2021
A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures journal November 2008
Translational energy dependence of Ar + +XY→ArX + +Y (XY=H 2 ,D 2 ,HD) from thermal to 30 eV c.m. journal July 1985
Guided Ion Beam and Quantum Chemical Investigation of the Thermochemistry of Thorium Dioxide Cations: Thermodynamic Evidence for Participation of f Orbitals in Bonding journal February 2020
Energy-Degeneracy-Driven Covalency in Actinide Bonding journal December 2018
Nonadiabatic unimolecular reactions. 1. A statistical formulation for the rate constants journal August 1988
State-Specific Reactions of Fe+(a6D,a4F) with D2O and Reactions of FeO+ with D2 journal June 1994
The Power of Accurate Energetics (or Thermochemistry: What is it Good for?) journal January 2013
Theoretical Study of Bond Distances and Dissociation Energies of Actinide Oxides AnO and AnO 2 journal April 2012
Bonding and bending in the actinyls journal February 1999
Thermochemistry and Structures of CoC3H6+: Metallacycle and Metal-Alkene Isomers journal September 1994
Evaluation of the Pr + O → PrO + + e − chemi-ionization reaction enthalpy and praseodymium oxide, carbide, dioxide, and carbonyl cation bond energies journal January 2021
Handbook of Basic Atomic Spectroscopic Data journal December 2005
Route to Chemical Accuracy for Computational Uranium Thermochemistry journal October 2022
Reactions of U + with H 2 , D 2 , and HD Studied by Guided Ion Beam Tandem Mass Spectrometry and Theory journal September 2021
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium † journal November 2009
Reactions of N+4 with rare gases from thermal to 10eV center-of-mass energy: collision-induced dissociation, charge transfer and ligand exchange journal June 1991
Guided Ion Beam Studies of the Reactions of Mn+, Cu+, and Zn+ with Silane. M+-SiHx (x = 0-3) Bond Energies journal February 1995
The Electronic Spectrum of the UO 2 Molecule journal January 2005
Guided ion-beam and theoretical studies of the reaction of Os+ (6D) with O2: Adiabatic and nonadiabatic behavior journal November 2013
Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy journal October 2006
Reactions of atomic thorium and uranium cations with CF4 studied by guided ion beam tandem mass spectrometry journal February 2022
Reactions of Gaseous Molecule Ions with Gaseous Molecules. V. Theory journal August 1958
Infrared Spectra of UO 2 , UO 2 + , and UO 2 - in Solid Neon journal June 2000

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
uranium dioxide cations
f orbitals
mass spectrometry
thermochemistry
bond dissociation energy
thermodynamics
computational models
threshold energy
collision-induced dissociation
guided ion ben mass spectrometry
chemical bonding
chemical reaction cross sections