Uranium-Induced Changes in Crystal-Field and Covalency Effects of Th4+ in Th1-xUxO2 Mixed Oxides Probed by High-Resolution X-ray Absorption Spectroscopy
文献类型：期刊论文
| 作者 | Bao, HL; Duan, PQ; Zhou, J; Cao, HJ; Li, J; Yu, HS; Jiang, Z; Liu, HT; Zhang, LJ; Lin, J |
| 刊名 | INORGANIC CHEMISTRY
 |
| 出版日期 | 2018 |
| 卷号 | 57期号:18页码:11404-11413 |
| 关键词 | DIOXIDE SOLID-SOLUTIONS LOCAL-STRUCTURE ELECTRONIC-STRUCTURE CHARGE-DISTRIBUTION ACTINIDE MATERIALS FINE-STRUCTURE THORIUM SPECTROMETER DISSOLUTION SCATTERING |
| ISSN号 | 0020-1669 |
| DOI | 10.1021/acs.inorgchem.8b01142 |
| 文献子类 | 期刊论文 |
| 英文摘要 | Knowledge of the local Th structure is a prerequisite for a better understanding of the physicochemical properties of the thorium-based mixed oxides (Th-MOX) involved in the Th-based nuclear fuel cycle. The crystalline electric field (CEF) splitting of the 6d shell in Th1-xUxO2 (x = 0.25, 0.5, 0.75) solid solution was probed by the Th L-3 edge high-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) collected at the L-beta s emission line, which cannot be obtained by conventional X-ray absorption methods. The detected CEF split between the 6d e(g) and t(2g) orbitals in ThO2 consisting of ordered Th-O-8 cubes with cubic symmetry is similar to 3.5 eV for the Th4+ ion. Because the split peaks of the white line corresponding to the crystal-field splitting of the unoccupied 6d states were resolved in the HERFD-XANES spectra, the analysis of these split peaks combined with first-principles calculations revealed that an increase of the U content involves the distortion of the Th-O-8 cubes in the Th1-xUxO2 mixed oxides. The lower symmetry of the Th-O-8 cube induced by the incorporated U tends to reduce the local crystal-field around Th4+ as well as the hybridization of Th 6t(2g)-O 2p which is mainly responsible for the covalent property of the Th-O bond. The phenomenon is noticeable in Th0.25U0.75O2, whose CEF splitting is decreased by approximately 10%, and covalent mixing between Th 6d t(2g) and O 2p orbitals is substantially reduced compared to that of pure ThO2. |
| 语种 | 英语 |
| 源URL | [http://ir.sinap.ac.cn/handle/331007/31173]  |
| 专题 | 上海应用物理研究所_中科院上海应用物理研究所2011-2017年 |
| 作者单位 | 1.Univ Saskatchewan, Canadian Light Source, Saskatoon, SK S7N 2V3, Canada 2.Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai 201800, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Bao, HL,Duan, PQ,Zhou, J,et al. Uranium-Induced Changes in Crystal-Field and Covalency Effects of Th4+ in Th1-xUxO2 Mixed Oxides Probed by High-Resolution X-ray Absorption Spectroscopy[J]. INORGANIC CHEMISTRY,2018,57(18):11404-11413. |
| APA | Bao, HL.,Duan, PQ.,Zhou, J.,Cao, HJ.,Li, J.,...&Wang, JQ.(2018).Uranium-Induced Changes in Crystal-Field and Covalency Effects of Th4+ in Th1-xUxO2 Mixed Oxides Probed by High-Resolution X-ray Absorption Spectroscopy.INORGANIC CHEMISTRY,57(18),11404-11413. |
| MLA | Bao, HL,et al."Uranium-Induced Changes in Crystal-Field and Covalency Effects of Th4+ in Th1-xUxO2 Mixed Oxides Probed by High-Resolution X-ray Absorption Spectroscopy".INORGANIC CHEMISTRY 57.18(2018):11404-11413. |
入库方式： OAI收割
来源：上海应用物理研究所
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