First-principles calculations of hematite (α-Fe2O3) by self-consistent DFT+U+V

Abstract

Summary: Owing to the confined Fe-3d orbitals and self-interaction error of exchange-correlation functionals, approximate DFT fails to describe iron oxides electronic structure and magnetic properties accurately. Hybrid DFT or DFT + U can solve these problems, but the former is expensive, and the latter only considers on-site interactions. Here, we used DFT + U + V, a DFT + U extension including inter-site interactions, to simulate the structural, magnetic, and electronic properties, along with Fe and O K-edge XAS spectra of α-Fe2O3. Two types of atomic orbital projectors were studied, orthogonalized and non-orthogonalized. DFT + U + V improves the description of the structural, magnetic, and electronic properties of α-Fe2O3 compared to approximate DFT. The accuracy of the correction depends on the orbital projector used. DFT + U + V with orthogonalized projectors achieves the best experimental agreement at a fraction of hybrid DFT cost. This work emphasizes the importance of inter-site interactions and the type of atomic orbital projectors used in the theoretical research of α-Fe2O3.

Keywords

• Magnetism
• Condensed matter properties
• Computational physics