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Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-02-08 , DOI: 10.1021/acs.jpcc.2c07771
Lucia Amidani 1, 2 , Thomas Dumas 3 , David K. Shuh 4 , Sergei M. Butorin 5 , Christoph J. Sahle 6 , Alessandro Longo 6 , Kristina O. Kvashnina 1, 2
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-02-08 , DOI: 10.1021/acs.jpcc.2c07771
Lucia Amidani 1, 2 , Thomas Dumas 3 , David K. Shuh 4 , Sergei M. Butorin 5 , Christoph J. Sahle 6 , Alessandro Longo 6 , Kristina O. Kvashnina 1, 2
Affiliation
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Experimental oxygen K-edge spectra of ThO2 and CeO2 are presented and interpreted based on density functional theory (DFT). The contribution of d and f orbitals to the O K-edge spectrum is identified as well-distinguished peaks, the presence of which evidences the strong hybridization of Th and Ce metal centers with O orbitals. The sensitivity of the O K-edge to both f- and d-states in the absence of a core–hole on the metal ion results in an insightful overview of the electronic structure involved in the chemical bond. In particular, the large bandwidth of the Th 5f band as compared to the Ce 4f band is observed as a set of wider and more substantial set of peaks in the O K-edge, confirming the stronger hybridization of the former with O orbitals. The peak ascribed to the 5f band of ThO2 is found at higher energy than the 6d band, as predicted from DFT calculations on actinide dioxides. To highlight the sensitivity and the potential use of the O K-edge for the characterization of ThO2-based systems, the sensitivity of the spectrum to structural changes such as lattice expansion and size reduction are calculated and discussed.
中文翻译：
ThO2 和 CeO2 的氧 K 边 X 射线吸收光谱：实验、解释和结构效应
ThO 2和CeO 2的实验氧K边谱基于密度泛函理论 (DFT) 提出和解释。d 和 f 轨道对 O K 边缘光谱的贡献被确定为清晰可辨的峰，其存在证明了 Th 和 Ce 金属中心与 O 轨道的强杂化。在金属离子上没有核孔的情况下，O K 边缘对 f 态和 d 态的敏感性导致对化学键中涉及的电子结构的深入了解。特别是，与 Ce 4f 带相比，Th 5f 带的大带宽被观察为 O K 边缘中一组更宽和更实质的峰，证实了前者与 O 轨道的更强杂化。ThO 2的 5f 带峰发现能量高于 6d 波段，如锕系元素二氧化物的 DFT 计算所预测的那样。为了突出 O K 边缘在基于 ThO 2的系统表征中的敏感性和潜在用途，计算并讨论了光谱对结构变化（例如晶格膨胀和尺寸减小）的敏感性。
更新日期：2023-02-08
中文翻译：
ThO2 和 CeO2 的氧 K 边 X 射线吸收光谱：实验、解释和结构效应
ThO 2和CeO 2的实验氧K边谱基于密度泛函理论 (DFT) 提出和解释。d 和 f 轨道对 O K 边缘光谱的贡献被确定为清晰可辨的峰，其存在证明了 Th 和 Ce 金属中心与 O 轨道的强杂化。在金属离子上没有核孔的情况下，O K 边缘对 f 态和 d 态的敏感性导致对化学键中涉及的电子结构的深入了解。特别是，与 Ce 4f 带相比，Th 5f 带的大带宽被观察为 O K 边缘中一组更宽和更实质的峰，证实了前者与 O 轨道的更强杂化。ThO 2的 5f 带峰发现能量高于 6d 波段，如锕系元素二氧化物的 DFT 计算所预测的那样。为了突出 O K 边缘在基于 ThO 2的系统表征中的敏感性和潜在用途，计算并讨论了光谱对结构变化（例如晶格膨胀和尺寸减小）的敏感性。
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