ArXiv · 2026
Rare-earth orthoferrites such as DyFeO₃ exhibit a rich interplay between localized rare-earth and transition-metal moments, giving rise to complex magnetic phases and magnetoelectric phenomena. Understanding their electronic and spectroscopic properties from first principles requires an accurate description of the localized Fe-3d and Dy-4f states and their hybridization with O-2p states. Here, we combine first-principles calculations and x-ray absorption near-edge structure (XANES) measurements to investigate the electronic structure and the O K-edge spectrum of DyFeO₃. We employ density-functional theory (DFT) with Hubbard U corrections (DFT+U) determined from first principles using density-functional perturbation theory, the HSE06 hybrid functional, and orbital-resolved DFT+U with Hubbard parameters calibrated to reproduce the electronic structure computed using HSE06. We find that standard DFT+U, despite improving the band gap, substantially underestimates the crystal-field splitting of the unoccupied Fe-3d states and consequently fails to accurately reproduce the separation of the two lowest-energy features in the O K-edge spectrum. HSE06 provides a more balanced description of the relevant electronic states, including the Fe-3d crystal-field splitting. Mapping the corresponding electronic structure onto orbital-resolved DFT+U yields a spectrum that remarkably reproduces the two lowest-energy experimental features and captures the main characteristics of the spectrum at higher energies. These results establish the low-energy O K-edge features as a sensitive probe of the Fe-3d crystal-field splitting, while showing that the localized Dy-4f states leave no distinct spectral fingerprints despite their importance for the magnetic properties.
Try inveni