Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory

Söderlind, Per; Landa, Alexander; Perron, Aurélien; Moore, Emily E.; Wu, Christine

doi:10.3390/app10186524

Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory

Journal Article · Fri Sep 18 00:00:00 EDT 2020 · Applied Sciences

DOI:https://doi.org/10.3390/app10186524· OSTI ID:1735804

^[1]; ^[1]; Perron, Aurélien ^[1]; ^[1]; Wu, Christine ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1735804

Report Number(s):: LLNL-JRNL--812905; 1020102

Journal Information:: Applied Sciences, Journal Name: Applied Sciences Journal Issue: 18 Vol. 10; ISSN 2076-3417

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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