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

TL;DR

This paper investigates the importance of relativistic effects in the electronic structure calculations of UO2 using DFT+U, showing that scalar-relativistic methods are sufficient for most properties, while full-relativistic calculations refine the results.

Contribution

It compares non-relativistic, scalar-relativistic, and full-relativistic DFT+U approaches for UO2, highlighting the significance of relativistic effects on structural and electronic properties.

Findings

Non-relativistic results deviate significantly from experiments.

Scalar-relativistic approach yields highly accurate geometric properties.

Full-relativistic calculations with spin-orbit effects slightly improve band gap and lattice constant accuracy.

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.