Publication date: Nov 30, 2023
We present a first-principles study of the low-temperature rhombohedral phase of BaTiO₃ using Hubbard-corrected density-functional theory. By employing density-functional perturbation theory, we compute the onsite Hubbard U for Ti(3d) states and the intersite Hubbard V between Ti(3d) and O(2p) states. We show that applying the onsite Hubbard U correction alone to Ti(3d) states proves detrimental, as it suppresses the Ti(3d)-O(2p) hybridization and drives the system towards a cubic phase. Conversely, when both onsite U and intersite V are considered, the localized character of the Ti(3d) states is maintained, while also preserving the Ti(3d)-O(2p) hybridization, restoring the rhombohedral phase of BaTiO₃. The generalized PBEsol+U+V functional yields good agreement with experimental results for the band gap and dielectric constant, while the optimized geometry is slightly less accurate compared to PBEsol. Zone-center phonon frequencies and Raman spectra are found to be significantly influenced by the underlying geometry. PBEsol and PBEsol+U+V provide satisfactory agreement with the experimental Raman spectrum when the PBEsol geometry is used, while PBEsol+U Raman spectrum diverges strongly from experimental data highlighting the adverse impact of the U correction alone in BaTiO₃. Our findings underscore the promise of the extended Hubbard PBEsol+U+V functional with first-principles U and V for the investigation of other ferroelectric perovskites with mixed ionic-covalent interactions.
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Files.tar
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26.7 MiB | Collection of all files which were used to produce the data of the paper: input files, output files, references to codes which were used, etc. |
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BaTiO3.aiida
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84.7 MiB | AiiDA data for BaTiO3 |
README_AiiDA.txt
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4.3 KiB | The README_AiiDA.txt file describes the content of the file "BaTiO3.aiida" |
2023.187 (version v1) [This version] | Nov 30, 2023 | DOI10.24435/materialscloud:vz-7q |