Relativistic effects in the study of structure and electronic properties of UO$_2$ within DFT+U method

Abstract

To study crystals that contain heavy atoms, it is important to consider the relativistic effects, as electrons in orbitals close to the atom's nucleus can reach speeds comparable to that of light in a vacuum. In this study, we utilized the first-principles DFT+U method to analyze the electronic structure and geometric properties of uranium dioxide (UO2) using three formulations: full-relativistic, scalar-relativistic, and non-relativistic. Our findings demonstrate that the non-relativistic scheme produces results that deviate significantly from experimental values for both lattice constant and band gap. In contrast, the scalar-relativistic regime yields highly accurate results for the geometric properties of UO2, and is therefore sufficient for most studies. However, for a more precise analysis, the full-relativistic calculations with spin-orbit effects should be employed, which result in a $6.2\%$ increase in the Kohn-Sham band-gap and a $0.05\%$ decrease in the lattice constant compared to the scalar-relativistic approach.