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High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds
Sergei M Butorin1, Kristina O Kvashnina2, Johan R Vegelius3
1Molecular and Condensed Matter Physics, Department of Physics and Astronomy, Uppsala University, SE-751 20 Uppsala, Sweden; sergei.butorin@physics.uu.se.
Abstract:
Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the [Formula: see text] shell directly in the HERFD-XAS spectra of actinides. Using ThO2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO2 is not an ionic compound as previously believed. The Th [Formula: see text] occupancy in the ground state was estimated to be twice that of the Th [Formula: see text] states. We demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.
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