Thermodynamics Modeling for Actinide Monocarbides and Mononitrides from First Principles

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.