Thermodynamics Modeling for Actinide Monocarbides and Mononitrides from First Principles

Söderlind, Per; Moore, Emily E.; Wu, Christine J.

doi:10.3390/app12020728

Thermodynamics Modeling for Actinide Monocarbides and Mononitrides from First Principles

Journal Article · Tue Jan 11 23:00:00 EST 2022 · Applied Sciences

DOI:https://doi.org/10.3390/app12020728· OSTI ID:1845635

^[1]; ^[1]; Wu, Christine J. ^[1]

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

The high-temperature thermodynamical properties for the actinide monocarbides and mononitrides ThC, ThN, UC, UN, PuC, and PuN are calculated from first-principles electronic-structure theory. The electronic structure is modeled with density-functional theory (DFT) and is fully relativistic, including the spin-orbit interaction. Furthermore, the DFT is extended to account for orbital–orbital interactions, by means of a parameter-free orbital-polarization (OP) technique, that has proven to be essential for the 5f electrons in plutonium. Strong anharmonicity and the temperature dependence of the lattice vibrations are captured with the self-consistent ab initio lattice dynamics (SCAILD) method. The calculated free energies and heat capacities are compared to published results from quasi-harmonic (QH) theory, and experiments, where available. For the uranium and plutonium compounds, we make use of CALPHAD assessments to help evaluate the theory. Generally, our anharmonic relativistic approach compares well with both CALPHAD and experiments. For the thorium compounds, our theory is in good accord with QH modeling of the free energy at lower temperatures but for the heat capacity the comparison is less favorable.

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:: 1845635

Report Number(s):: LLNL-JRNL-829554; 1045461

Journal Information:: Applied Sciences, Journal Name: Applied Sciences Journal Issue: 2 Vol. 12; ISSN 2076-3417

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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