Ab initio modeling and thermodynamics of hydrated plutonium oxalates

Michael D. LaCount; David E. Meier; Andrew M. Ritzmann; Scott E. Muller; Richard A. Clark; Edgar C. Buck; David G. Abrecht

doi:10.1016/j.jnucmat.2023.154504

Ab initio modeling and thermodynamics of hydrated plutonium oxalates

Michael D. LaCount, David E. Meier, Andrew M. Ritzmann, Scott E. Muller, Richard A. Clark, Edgar C. Buck, David G. Abrecht

Collection Science and Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

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. 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.

Original language	English
Article number	154504
Journal	Journal of Nuclear Materials
Volume	583
DOIs	https://doi.org/10.1016/j.jnucmat.2023.154504
State	Published - Sep 2023

Funding

This work was supported by the National Technical Nuclear Forensics Center in DHS's Countering Weapons of Mass Destruction Office (DHS-CWMD) and conducted at Pacific Northwest National Laboratory. The research was performed using resources available through Research Computing at Pacific Northwest National Laboratory (PNNL). This work was performed at Pacific Northwest National Laboratory, which is operated by the Battelle Memorial Institute for the U. S. Department of Energy under Contract No. DE-AC05-76RL0-1830.

Funders	Funder number
Countering Weapons of Mass Destruction Office
DHS-CWMD
National Technical Nuclear Forensics Center
U.S. Department of Energy	DE-AC05-76RL0-1830

Access to Document

10.1016/j.jnucmat.2023.154504

Cite this

@article{094fe67950ac4f239f43406ea434d136,

title = "Ab initio modeling and thermodynamics of hydrated plutonium oxalates",

abstract = "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. 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.",

author = "LaCount, {Michael D.} and Meier, {David E.} and Ritzmann, {Andrew M.} and Muller, {Scott E.} and Clark, {Richard A.} and Buck, {Edgar C.} and Abrecht, {David G.}",

note = "Publisher Copyright: {\textcopyright} 2023",

year = "2023",

month = sep,

doi = "10.1016/j.jnucmat.2023.154504",

language = "English",

volume = "583",

journal = "Journal of Nuclear Materials",

issn = "0022-3115",

publisher = "Elsevier",

}

TY - JOUR

T1 - Ab initio modeling and thermodynamics of hydrated plutonium oxalates

AU - LaCount, Michael D.

AU - Meier, David E.

AU - Ritzmann, Andrew M.

AU - Muller, Scott E.

AU - Clark, Richard A.

AU - Buck, Edgar C.

AU - Abrecht, David G.

PY - 2023/9

Y1 - 2023/9

N2 - 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. 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.

AB - 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. 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.

UR - http://www.scopus.com/inward/record.url?scp=85162260774&partnerID=8YFLogxK

U2 - 10.1016/j.jnucmat.2023.154504

DO - 10.1016/j.jnucmat.2023.154504

M3 - Article

AN - SCOPUS:85162260774

SN - 0022-3115

VL - 583

JO - Journal of Nuclear Materials

JF - Journal of Nuclear Materials

M1 - 154504

ER -

Ab initio modeling and thermodynamics of hydrated plutonium oxalates

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this