Benchmark of First-Principles Titanium K-Edge X-Ray Absorption Spectral Simulations on Titanium-containing Oxides
Abstract
X-ray absorption spectroscopy (XAS) is a powerful, element-specific probe for investigating the local structural and electronic properties of materials. However, quantitative analysis remains challenging, necessitating accurate first-principles spectral simulations. In this study, we benchmark first-principles simulations of Ti K-edge X-ray absorption near-edge structure (XANES) against experimental data for nine common titanium compounds. We systematically investigate key physical effects, including quadrupole excitations, thermal disorder, and many-body shake-up. Our results demonstrate that quadrupole excitations and thermal disorder are essential for capturing accurate pre-edge features, while many-body shake-up effects significantly influence the spectral shape of the main- and post-edge regions. By incorporating these effects alongside a band-theory treatment of the core-hole final state, our simulated spectra achieve excellent agreement with experimental data for most of the systems, as evidenced by high similarity scores. The shoulder peak in BaTiO3 at 4980 eV in the experiment is largely missing in simulation. Further analysis shows that more accurate electronic structure theory than semi-local density functional theory is required to capture the correlation effects of the Ba 4f orbitals and that defects, such as oxygen vacancies, may also contribute to the shoulder. Beyond tackling specific titanium material systems, this work establishes a robust workflow for generating high-fidelity Ti K-edge XANES databases for titanium compounds, providing a framework that can be generalized to a broad range of materials.
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BibTeX
@misc{cao2026benchmark,
title = {{Benchmark of First-Principles Titanium K-Edge X-Ray Absorption Spectral Simulations on Titanium-containing Oxides}},
author = {Chuntian Cao and Joshua J. Kas and Karol Dyro and Bruce Ravel and John Vinson and Deyu Lu},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.33776},
eprint = {2609.33776},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.33776},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Benchmark of First-Principles Titanium K-Edge X-Ray Absorption Spectral Simulations on Titanium-containing Oxides
AU - Chuntian Cao
AU - Joshua J. Kas
AU - Karol Dyro
AU - Bruce Ravel
AU - John Vinson
AU - Deyu Lu
PY - 2026
DA - 2026/09/27
PB - arXiv
DO - 10.48550/arxiv.2609.33776
UR - https://arxiv.org/abs/2609.33776
AB - X-ray absorption spectroscopy (XAS) is a powerful, element-specific probe for investigating the local structural and electronic properties of materials. However, quantitative analysis remains challenging, necessitating accurate first-principles spectral simulations. In this study, we benchmark first-principles simulations of Ti K-edge X-ray absorption near-edge structure (XANES) against experimental data for nine common titanium compounds. We systematically investigate key physical effects, including quadrupole excitations, thermal disorder, and many-body shake-up. Our results demonstrate that quadrupole excitations and thermal disorder are essential for capturing accurate pre-edge features, while many-body shake-up effects significantly influence the spectral shape of the main- and post-edge regions. By incorporating these effects alongside a band-theory treatment of the core-hole final state, our simulated spectra achieve excellent agreement with experimental data for most of the systems, as evidenced by high similarity scores. The shoulder peak in BaTiO_3 at 4980 eV in the experiment is largely missing in simulation. Further analysis shows that more accurate electronic structure theory than semi-local density functional theory is required to capture the correlation effects of the Ba 4f orbitals and that defects, such as oxygen vacancies, may also contribute to the shoulder. Beyond tackling specific titanium material systems, this work establishes a robust workflow for generating high-fidelity Ti K-edge XANES databases for titanium compounds, providing a framework that can be generalized to a broad range of materials.
ER -