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Ab initio modeling and thermodynamics of hydrated plutonium oxalates

Journal Article · · Journal of Nuclear Materials
 [1];  [1];  [1];  [1];  [1];  [1];  [2]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  2. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
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An ab initio study on the plutonium oxalate hydrates: Pu2(C2O4)3·10H2O and Pu(C2O4)2·6H2O, using PBE exchange-correlation with D3 dispersion correction and Hubbard correction for the plutonium atoms, was performed and compared to experimental vibrational spectral and thermodynamic property values. Here we demonstrated that this technique can accurately predict the experimental infrared spectra Pu(III) oxalate hydrate, as well as the Raman peak of PuO2 (used to calculate the thermodynamic properties of the oxalates). For Pu(IV) oxalate hydrate we found that our predicted structure agreed qualitatively with PXRD measurements, the only available experimental determination of the structure. Using this method at standard temperature and pressure, we predicted standard enthalpies of formation of -6,755 kJ mol-1 and -3,923 kJ mol-1 and standard Gibbs free energy of formation of -5,899 kJ mol-1 and -3,386 kJ mol-1 for Pu2(C2O4)3·10H2O and Pu(C2O4)2·6H2O, respectively.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
Department of Homeland Security (DHS); USDOE
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1988226
Report Number(s):
PNNL-SA-178539
Journal Information:
Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 583; ISSN 0022-3115
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE