Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory
Abstract
Thermodynamics of plutonium monocarbide is studied from first-principles theory that includes relativistic electronic structure and anharmonic lattice vibrations. Density-functional theory (DFT) is expanded to include orbital-orbital coupling in addition to the relativistic spin-orbit interaction for the electronic structure and it is combined with anharmonic, temperature dependent, lattice dynamics derived from the self-consistent ab initio lattice dynamics (SCAILD) method. The obtained thermodynamics are compared to results from simpler quasi-harmonic theory and experimental data. Formation enthalpy, specific heat, and Gibbs energy calculated from the anharmonic model are validated by direct comparison with a calculation of phase diagram (CALPHAD) assessment of PuC and sub-stochiometric PuC0.896. Overall, the theory reproduces CALPHAD results and measured data for PuC rather well, but the comparison is hampered by the sub-stoichiometric nature of plutonium monocarbide. It was found that a bare theoretical approach that ignores spin-orbit and orbital-orbital coupling (orbital polarization) of the plutonium 5f electrons promotes too soft phonons and Gibbs energies that are incompatible with that of the CALPHAD assessment of the experimental data. The investigation of PuC suggests that the electronic structure is accurately described by plutonium 5f electrons as “band like” and delocalized, but correlate through spin polarization, orbital polarization, and spin-orbit coupling, inmore »
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1735804
- Report Number(s):
- LLNL-JRNL-812905
Journal ID: ISSN 2076-3417; 1020102; TRN: US2205256
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Sciences
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 18; Journal ID: ISSN 2076-3417
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; PuC; DFT; CALPHAD; electron correlation; anharmonic phonons; thermodynamics; nuclear fuel
Citation Formats
Söderlind, Per, Landa, Alexander, Perron, Aurélien, Moore, Emily E., and Wu, Christine. Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory. United States: N. p., 2020.
Web. doi:10.3390/app10186524.
Söderlind, Per, Landa, Alexander, Perron, Aurélien, Moore, Emily E., & Wu, Christine. Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory. United States. https://doi.org/10.3390/app10186524
Söderlind, Per, Landa, Alexander, Perron, Aurélien, Moore, Emily E., and Wu, Christine. Fri .
"Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory". United States. https://doi.org/10.3390/app10186524. https://www.osti.gov/servlets/purl/1735804.
@article{osti_1735804,
title = {Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory},
author = {Söderlind, Per and Landa, Alexander and Perron, Aurélien and Moore, Emily E. and Wu, Christine},
abstractNote = {Thermodynamics of plutonium monocarbide is studied from first-principles theory that includes relativistic electronic structure and anharmonic lattice vibrations. Density-functional theory (DFT) is expanded to include orbital-orbital coupling in addition to the relativistic spin-orbit interaction for the electronic structure and it is combined with anharmonic, temperature dependent, lattice dynamics derived from the self-consistent ab initio lattice dynamics (SCAILD) method. The obtained thermodynamics are compared to results from simpler quasi-harmonic theory and experimental data. Formation enthalpy, specific heat, and Gibbs energy calculated from the anharmonic model are validated by direct comparison with a calculation of phase diagram (CALPHAD) assessment of PuC and sub-stochiometric PuC0.896. Overall, the theory reproduces CALPHAD results and measured data for PuC rather well, but the comparison is hampered by the sub-stoichiometric nature of plutonium monocarbide. It was found that a bare theoretical approach that ignores spin-orbit and orbital-orbital coupling (orbital polarization) of the plutonium 5f electrons promotes too soft phonons and Gibbs energies that are incompatible with that of the CALPHAD assessment of the experimental data. The investigation of PuC suggests that the electronic structure is accurately described by plutonium 5f electrons as “band like” and delocalized, but correlate through spin polarization, orbital polarization, and spin-orbit coupling, in analogy to previous findings for plutonium metal.},
doi = {10.3390/app10186524},
journal = {Applied Sciences},
number = 18,
volume = 10,
place = {United States},
year = {Fri Sep 18 00:00:00 EDT 2020},
month = {Fri Sep 18 00:00:00 EDT 2020}
}
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