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• W2013659337 abstract "Fourier transform ion cyclotron resonance mass spectrometry was employed to study the products and kinetics of gas-phase reactions of Cm+ and Cm2+; parallel studies were carried out with La+/2+, Gd+/2+ and Lu+/2+. Reactions with oxygen-donor molecules provided estimates for the bond dissociation energies, D[M+−O] (M = Cm, Gd, Lu). The first ionization energy, IE[CmO], was obtained from the reactivity of CmO+ with dienes, and the second ionization energies, IE[MO+] (M = Cm, La, Gd, Lu), from the rates of electron-transfer reactions from neutrals to the MO2+ ions. The following thermodynamic quantities for curium oxide molecules were obtained: IE[CmO] = 6.4 ± 0.2 eV; IE[CmO+] = 15.8 ± 0.4 eV; D[Cm−O] = 710 ± 45 kJ mol−1; D[Cm+−O] = 670 ± 40 kJ mol−1; and D[Cm2+−O] = 342 ± 55 kJ mol−1. Estimates for the M2+−O bond energies for M = Cm, La, Gd, and Lu are all intermediate between D[N2−O] and D[OC−O] − that is, 167 kJ mol−1 < D[M2+−O] < 532 kJ mol−1 − such that the four MO2+ ions fulfill the thermodynamic requirement for catalytic oxygen-atom transport from N2O to CO. It was demonstrated that the kinetics are also favorable and that the CmO2+, LaO2+, GdO2+, and LuO2+ dipositive ions each catalyze the gas-phase oxidation of CO to CO2 by N2O. The CmO2+ ion appeared during the reaction of Cm+ with O2 when the intermediate, CmO+, was not collisionally cooled − although its formation is kinetically and/or thermodynamically unfavorable, CmO2+ is a stable species." @default.
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• W2013659337 date "2008-10-16" @default.
• W2013659337 modified "2023-09-24" @default.
• W2013659337 title "Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO" @default.
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• W2013659337 doi "https://doi.org/10.1021/jp8047899" @default.
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