1 Theory and Simulation of Materials (THEOS), and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland
2 nanotech@surfaces Laboratory and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), Empa - Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
3 Electron Microscopy Center, Empa - Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
4 nanotech@surfaces Laboratory, Empa - Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
5 State Key Laboratory of Metastable Material Science and Technology, Yanshan University, CN-066004 Qinhuangdao, China
6 High Performance Ceramics Laboratory, Empa - Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland
7 Department for Materials, Nonmetallic Inorganic Materials, ETH Zurich, Swiss Federal Institute of Technology, CH-8037 Zurich, Switzerland
8 Vocational School of Technical Sciences, Department of Medical Services and Techniques, Program of Opticianry, Mersin University, TR-33343 Yenisehir, Mersin, Turkey
9 Advanced Technology Education Research and Application Center, Mersin University, TR-33343 Yenisehir, Mersin, Turkey
10 Department of Physics, University of Pavia, via Bassi 6, I-27100 Pavia, Italy
11 Dipartmento di Fisica, Università di Trento, via Sommarive 14, 38123 Povo, Italy
12 Sorbonne Université, CNRS, Institut des Nanosciences de Paris, UMR7588, F-75252 Paris, France
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How to cite this record
Electronic structure of pristine and Ni-substituted LaFeO₃ from near edge x-ray absorption fine structure experiments and first-principles simulations
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We present a joint theoretical and experimental study of the oxygen K-edge spectra for LaFeO₃ and homovalent Ni-substituted LaFeO₃ (LaFe₀.₇₅Ni₀.₂₅O₃), using first-principles simulations based on density-functional theory with extended Hubbard functionals and x-ray absorption near edge structure (XANES) measurements. Ground-state and excited-state XANES calculations employ Hubbard on-site U and inter-site V parameters determined from first principles and the Lanczos recursive method to obtain absorption cross sections, which allows for a reliable description of XANES spectra in transition-metal compounds in a very broad energy range, with an accuracy comparable to that of hybrid functionals but at a substantially lower cost. We show that standard gradient-corrected exchange-correlation functionals fail in capturing accurately the electronic properties of both materials. In particular, for LaFe₀.₇₅Ni₀.₂₅O₃ they do not reproduce its semiconducting behaviour and provide a poor description of the pre-edge features at the O K edge. The inclusion of Hubbard interactions leads to a drastic improvement, accounting for the semiconducting ground state of LaFe₀.₇₅Ni₀.₂₅O₃ and for good agreement between calculated and measured XANES spectra. We show that the partial substitution of Ni for Fe affects the conduction-band bottom by generating a strongly hybridized O(2p)-Ni(3d) minority-spin empty electronic state. The present work, based on a consistent correction of self-interaction errors, outlines the crucial role of extended Hubbard functionals to describe the electronic structure of complex transition-metal oxides such as LaFeO₃ and LaFe₀.₇₅Ni₀.₂₅O₃ and paves the way to future studies on similar systems.
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Preprint (Preprint where the data is discussed)
I. Timrov, P. Agrawal, X. Zhang, S. Erat, R. Liu, A. Braun, M. Cococcioni, M. Calandra, N. Marzari, D. Passerone, arXiv:2004.04142 (2020)