Unraveling the electronic structure and the oxygen K-edge x-ray absorption near-edge structure spectrum of DyFeO3
Abstract
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.
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BibTeX
@misc{gebreyesus2026unraveling,
title = {{Unraveling the electronic structure and the oxygen $K$-edge x-ray absorption near-edge structure spectrum of DyFeO$_3$}},
author = {G. Gebreyesus and Eric Macke and Pietro Delugas and Weiguo Jing and Banani Biswas and Carlos A. F. Vaz and Christof W. Schneider and Iurii Timrov},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.31079},
eprint = {2609.31079},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.31079},
}
RIS
TY - UNPB
TI - Unraveling the electronic structure and the oxygen K-edge x-ray absorption near-edge structure spectrum of DyFeO_3
AU - G. Gebreyesus
AU - Eric Macke
AU - Pietro Delugas
AU - Weiguo Jing
AU - Banani Biswas
AU - Carlos A. F. Vaz
AU - Christof W. Schneider
AU - Iurii Timrov
PY - 2026
DA - 2026/09/25
PB - arXiv
DO - 10.48550/arxiv.2609.31079
UR - https://arxiv.org/abs/2609.31079
AB - Rare-earth orthoferrites such as DyFeO_3 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 DyFeO_3. 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.
ER -