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锕系元素M边和配体K边的高能分辨X射线光谱学:我们已知的、我们想知道的以及我们能够知道的。

High-energy resolution X-ray spectroscopy at actinide M and ligand K edges: what we know, what we want to know, and what we can know.

作者信息

Kvashnina Kristina O, Butorin Sergei M

机构信息

The Rossendorf Beamline at ESRF, The European Synchrotron, CS40220, 38043 Grenoble Cedex 9, France.

Institute of Resource Ecology, Helmholtz Zentrum Dresden-Rossendorf (HZDR), PO Box 510119, 01314 Dresden, Germany.

出版信息

Chem Commun (Camb). 2022 Jan 4;58(3):327-342. doi: 10.1039/d1cc04851a.

Abstract

In recent years, scientists have progressively recognized the role of electronic structures in the characterization of chemical properties for actinide containing materials. High-energy resolution X-ray spectroscopy at the actinide M edges emerged as a promising direction because this method can probe actinide properties at the atomic level through the possibility of reducing the experimental spectral width below the natural core-hole lifetime broadening. Parallel to the technical developments of the X-ray method and experimental discoveries, theoretical models, describing the observed electronic structure phenomena, have also advanced. In this feature article, we describe the latest progress in the field of high-energy resolution X-ray spectroscopy at the actinide M and ligand K edges and we show that the methods are able to (a) provide fingerprint information on the actinide oxidation state and ground state characters (b) probe 5f occupancy, non-stoichiometry, defects, and ligand/metal ratio and (c) investigate the local symmetry and effects of the crystal field. We discuss the chemical aspects of the electronic structure in terms familiar to chemists and materials scientists and conclude with a brief description of new opportunities and approaches to improve the experimental methodology and theoretical analysis for f-electron systems.

摘要

近年来,科学家们逐渐认识到电子结构在含锕系元素材料化学性质表征中的作用。锕系元素M边的高能分辨X射线光谱学成为一个有前景的方向,因为这种方法能够通过将实验光谱宽度降低到自然芯孔寿命展宽以下,在原子水平上探测锕系元素的性质。与X射线方法的技术发展和实验发现并行,描述所观察到的电子结构现象的理论模型也取得了进展。在这篇专题文章中,我们描述了锕系元素M边和配体K边高能分辨X射线光谱学领域的最新进展,并且我们表明这些方法能够:(a) 提供关于锕系元素氧化态和基态特征的指纹信息;(b) 探测5f占据、非化学计量比、缺陷以及配体/金属比;(c) 研究局部对称性和晶体场效应。我们用化学家和材料科学家熟悉的术语讨论电子结构的化学方面,并最后简要描述改善f电子系统实验方法和理论分析的新机遇和途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a983/8725612/4dba95f5e3f2/d1cc04851a-f1.jpg

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