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Title: High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

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 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO 2 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 ThO 2 is not an ionic compound as previously believed. The Th 6d occupancy in the ground state was estimated to be twice that of the Th 5f states. Here, 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.

Authors:
 [1];  [2];  [1];  [3];  [4]
  1. Uppsala Univ. (Sweden). Molecular and Condensed Matter Physics, Dept. of Physics and Astronomy
  2. European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Resource Ecology
  3. Inst. de Chimie Separative de Marcoule, Centre de Marcoule (France)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1379524
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 29; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; covalency; crystal field; actinide compounds

Citation Formats

Butorin, Sergei M., Kvashnina, Kristina O., Vegelius, Johan R., Meyer, Daniel, and Shuh, David K. High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds. United States: N. p., 2016. Web. doi:10.1073/pnas.1601741113.
Butorin, Sergei M., Kvashnina, Kristina O., Vegelius, Johan R., Meyer, Daniel, & Shuh, David K. High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds. United States. https://doi.org/10.1073/pnas.1601741113
Butorin, Sergei M., Kvashnina, Kristina O., Vegelius, Johan R., Meyer, Daniel, and Shuh, David K. Fri . "High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds". United States. https://doi.org/10.1073/pnas.1601741113. https://www.osti.gov/servlets/purl/1379524.
@article{osti_1379524,
title = {High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds},
author = {Butorin, Sergei M. and Kvashnina, Kristina O. and Vegelius, Johan R. and Meyer, Daniel and Shuh, David K.},
abstractNote = {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 5f 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 6d occupancy in the ground state was estimated to be twice that of the Th 5f states. Here, 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.},
doi = {10.1073/pnas.1601741113},
url = {https://www.osti.gov/biblio/1379524}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 29,
volume = 113,
place = {United States},
year = {2016},
month = {7}
}

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Cited by: 11 works
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    journal, July 2017


    A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants
    journal, November 2017


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