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 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.
- Authors:
-
- Uppsala Univ. (Sweden). Molecular and Condensed Matter Physics, Dept. of Physics and Astronomy
- European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf, Dresden (Germany). Inst. of Resource Ecology
- Inst. de Chimie Separative de Marcoule, Centre de Marcoule (France)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (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:
- 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},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 29,
volume = 113,
place = {United States},
year = {Fri Jul 01 00:00:00 EDT 2016},
month = {Fri Jul 01 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Role of resonant inelastic X-ray scattering in high-resolution core-level spectroscopy of actinide materials
journal, June 2014
- Kvashnina, K. O.; Kvashnin, Y. O.; Butorin, S. M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex
journal, February 2012
- Seaman, Lani A.; Wu, Guang; Edelstein, Norman
- Journal of the American Chemical Society, Vol. 134, Issue 10
Effect of spin-orbit coupling on the actinide dioxides AnO 2 (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study
journal, October 2012
- Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E.
- The Journal of Chemical Physics, Vol. 137, Issue 15
Non-aqueous Synthesis of Isotropic and Anisotropic Actinide Oxide Nanocrystals
journal, May 2012
- Hudry, Damien; Apostolidis, Christos; Walter, Olaf
- Chemistry - A European Journal, Vol. 18, Issue 27
Actinide and rare earth ions in single crystals of ThO2: Preparation, EPR studies and related problems
journal, August 1986
- Amoretti, G.; Giori, D. C.; Ori, O.
- Journal of the Less Common Metals, Vol. 122
Optical Spectra and Electronic Structure
book, January 2010
- Liu, Guokui; Beitz, James V.
- The Chemistry of the Actinide and Transactinide Elements
Theory of x-ray-absorption spectra in and some other rare-earth compounds
journal, January 1991
- Ogasawara, H.; Kotani, A.; Okada, K.
- Physical Review B, Vol. 43, Issue 1
Many-body effects in core-level spectroscopy of rare-earth compounds
journal, February 1988
- Kotani, A.; Jo, T.; Parlebas, J. C.
- Advances in Physics, Vol. 37, Issue 1
The ESRF beamline ID26: X-ray absorption on ultra dilute sample
journal, May 1999
- Gauthier, C.; Solé, V. A.; Signorato, R.
- Journal of Synchrotron Radiation, Vol. 6, Issue 3
Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles
journal, July 2005
- Nilsson, Hans J.; Tyliszczak, Tolek; Wilson, Richard E.
- Analytical and Bioanalytical Chemistry, Vol. 383, Issue 1
Localized Magnetic States in Metals
journal, October 1961
- Anderson, P. W.
- Physical Review, Vol. 124, Issue 1
The unoccupied electronic structure characterization of hydrothermally grown ThO 2 single crystals : The unoccupied electronic structure characterization of hydrothermally grown ThO
journal, January 2014
- Kelly, T. D.; Petrosky, J. C.; Turner, D.
- physica status solidi (RRL) - Rapid Research Letters, Vol. 8, Issue 3
Chemical State of Complex Uranium Oxides
journal, December 2013
- Kvashnina, K. O.; Butorin, S. M.; Martin, P.
- Physical Review Letters, Vol. 111, Issue 25
Electronic structure of the light actinide oxides from electron spectroscopy (invited)
journal, April 1988
- Gunnarsson, O.; Sarma, D. D.; Hillebrecht, F. U.
- Journal of Applied Physics, Vol. 63, Issue 8
Orbital Specificity in the Unoccupied States of from Resonant Inverse Photoelectron Spectroscopy
journal, October 2011
- Tobin, J. G.; Yu, S. -W.
- Physical Review Letters, Vol. 107, Issue 16
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005
- Glatzel, Pieter; Bergmann, Uwe
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
Core-level lifetimes as determined by x-ray photoelectron spectroscopy measurements
journal, October 1980
- Fuggle, John C.; Alvarado, Santos F.
- Physical Review A, Vol. 22, Issue 4
Configuration dependence of hopping matrix elements in the Anderson model
journal, August 1988
- Gunnarsson, O.; Jepsen, O.
- Physical Review B, Vol. 38, Issue 5
Spectroscopic studies and crystal-field analyses of and in the cubic-symmetry site of
journal, September 1993
- Hubert, S.; Thouvenot, P.; Edelstein, N.
- Physical Review B, Vol. 48, Issue 9
to atomic level widths of thorium and uranium as inferred from measurements of L and M x-ray spectra
journal, December 1999
- Raboud, P. -A.; Dousse, J. -Cl.; Hoszowska, J.
- Physical Review A, Vol. 61, Issue 1
Application of density functional theory in assessing properties of thoria and recycled fuels
journal, August 2013
- Szpunar, B.; Szpunar, J. A.
- Journal of Nuclear Materials, Vol. 439, Issue 1-3
Resonant X-Ray Fluorescence Spectroscopy of Correlated Systems: A Probe of Charge-Transfer Excitations
journal, July 1996
- Butorin, S. M.; Mancini, D. C.; Guo, J. -H.
- Physical Review Letters, Vol. 77, Issue 3
Sensitivity to Actinide Doping of Uranium Compounds by Resonant Inelastic X-ray Scattering at Uranium L 3 Edge
journal, August 2015
- Kvashnina, Kristina O.; Kvashnin, Yaroslav O.; Vegelius, Johan R.
- Analytical Chemistry, Vol. 87, Issue 17
Potential-Barrier Effects in Photoabsorption. II. Interpretation of Photoabsorption Resonances in Lanthanide Metals at the -Electron Threshold
journal, March 1972
- Sugar, Jack
- Physical Review B, Vol. 5, Issue 5
Performance of a high resolution, high flux density SGM undulator beamline at the ALS (invited)
journal, February 1995
- Warwick, Tony; Heimann, Phil; Mossessian, Dmitri
- Review of Scientific Instruments, Vol. 66, Issue 2
Theory of core-level spectroscopy in actinide systems
journal, May 1993
- Kotani, Akio; Ogasawara, Haruhiko
- Physica B: Condensed Matter, Vol. 186-188
Spectroscopic study and crystal-field analysis of in the cubic-symmetry site of
journal, October 1994
- Thouvenot, P.; Hubert, S.; Edelstein, N.
- Physical Review B, Vol. 50, Issue 14
Crystal fields in UO 2 - revisited
journal, November 2010
- Nakotte, H.; Rajaram, R.; Kern, S.
- Journal of Physics: Conference Series, Vol. 251
5 f -electron states in uranium dioxide investigated using high-resolution neutron spectroscopy
journal, July 1989
- Amoretti, G.; Blaise, A.; Caciuffo, R.
- Physical Review B, Vol. 40, Issue 3
Resonant inelastic X-ray scattering as a probe of optical scale excitations in strongly electron-correlated systems: quasi-localized view
journal, October 2000
- Butorin, Sergei M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 110-111
Mechanical and electronic properties of , , and alloys
journal, July 2009
- Sevik, C.; Çağın, T.
- Physical Review B, Vol. 80, Issue 1
The Theory of Complex Spectra
journal, November 1929
- Slater, J. C.
- Physical Review, Vol. 34, Issue 10
Oxidation and aging in U and Pu probed by spin-orbit sum rule analysis: Indications for covalent metal-oxide bonds
journal, January 2006
- Moore, K. T.; van der Laan, G.; Haire, R. G.
- Physical Review B, Vol. 73, Issue 3
Thorium/uranium mixed oxide nanocrystals: Synthesis, structural characterization and magnetic properties
journal, November 2013
- Hudry, Damien; Griveau, Jean-Christophe; Apostolidis, Christos
- Nano Research, Vol. 7, Issue 1
Theory of Polarization Dependence in Resonant X-Ray Emission Spectra of a Uranium Compound
journal, April 2002
- Nakazawa, Makoto; Ogasawara, Haruhiko; Kotani, Akio
- Surface Review and Letters, Vol. 09, Issue 02
Near-edge x-ray-absorption fine structure in uranium compounds
journal, February 1987
- Kalkowski, G.; Kaindl, G.; Brewer, W. D.
- Physical Review B, Vol. 35, Issue 6
Spin-mixed ground state of Fe phthalocyanine and the temperature-dependent branching ratio in X-ray absorption spectroscopy
journal, August 1988
- Thole, B. T.; Van Der Laan, G.; Butler, P. H.
- Chemical Physics Letters, Vol. 149, Issue 3
X-ray absorption and dichroism of transition metals and their compounds
journal, August 1994
- de Groot, F. M. F.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 67, Issue 4
The Theory of Atomic Structure and Spectra
book, December 1981
- Cowan, Robert D.
- Los Alamos Series in Basic and Applied Sciences, Vol. 3
Works referencing / citing this record:
The role of the 5f valence orbitals of early actinides in chemical bonding
journal, July 2017
- Vitova, T.; Pidchenko, I.; Fellhauer, D.
- Nature Communications, Vol. 8, Issue 1
A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants
journal, November 2017
- Li, Yuxiang; Yang, Zaixing; Wang, Yanlong
- Nature Communications, Vol. 8, Issue 1
Heteroleptic samarium( iii ) halide complexes probed by fluorescence-detected L 3 -edge X-ray absorption spectroscopy
journal, January 2018
- Goodwin, Conrad A. P.; Réant, Benjamin L. L.; Kragskow, Jon G. C.
- Dalton Transactions, Vol. 47, Issue 31
Measurements of the band gap of by electron spectroscopy techniques
journal, October 2019
- Gouder, T.; Eloirdi, R.; Martin, R. L.
- Physical Review Research, Vol. 1, Issue 3
The role of the 5f valence orbitals of early actinides in chemical bonding
text, January 2017
- Vitova, T.; Pidchenko, I.; Fellhauer, D.
- Karlsruhe
A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants
journal, November 2017
- Li, Yuxiang; Yang, Zaixing; Wang, Yanlong
- Nature Communications, Vol. 8, Issue 1