Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy
Abstract
Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree of the 5f localization in UO2. The results support the covalent character of UO2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.
- Authors:
-
- Uppsala Univ. (Sweden). Dept. of Physics and Astronomy
- European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Inst. of Resource Ecology, Dresden (Germany)
- 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). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1436141
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 51; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 47 OTHER INSTRUMENTATION
Citation Formats
Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Kvashnina, Kristina O., and Shuh, David K. Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy. United States: N. p., 2016.
Web. doi:10.1021/acs.jpcc.6b09335.
Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Kvashnina, Kristina O., & Shuh, David K. Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy. United States. https://doi.org/10.1021/acs.jpcc.6b09335
Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Kvashnina, Kristina O., and Shuh, David K. Wed .
"Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy". United States. https://doi.org/10.1021/acs.jpcc.6b09335. https://www.osti.gov/servlets/purl/1436141.
@article{osti_1436141,
title = {Probing Chemical Bonding in Uranium Dioxide by Means of High-Resolution X-ray Absorption Spectroscopy},
author = {Butorin, Sergei M. and Modin, Anders and Vegelius, Johan R. and Kvashnina, Kristina O. and Shuh, David K.},
abstractNote = {Here, a systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree of the 5f localization in UO2. The results support the covalent character of UO2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.},
doi = {10.1021/acs.jpcc.6b09335},
journal = {Journal of Physical Chemistry. C},
number = 51,
volume = 120,
place = {United States},
year = {Wed Nov 30 00:00:00 EST 2016},
month = {Wed Nov 30 00:00:00 EST 2016}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Effect of Mott-Hubbard correlations on the electronic structure and structural stability of uranium dioxide
journal, May 1997
- Dudarev, S. L.; Manh, D. Nguyen; Sutton, A. P.
- Philosophical Magazine B, Vol. 75, Issue 5
Oxidation and crystal field effects in uranium
journal, July 2015
- Tobin, J. G.; Yu, S. -W.; Booth, C. H.
- Physical Review B, Vol. 92, Issue 3
Electronic structure and core-level spectra of light actinide dioxides in the dynamical mean-field theory
journal, August 2015
- Kolorenč, Jindřich; Shick, Alexander B.; Lichtenstein, Alexander I.
- Physical Review B, Vol. 92, Issue 8
Resonance photoemission for f -electron systems
journal, December 1987
- Gunnarsson, O.; Li, T. C.
- Physical Review B, Vol. 36, Issue 18
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
Theory of core-level spectroscopy in actinide systems
journal, May 1993
- Kotani, Akio; Ogasawara, Haruhiko
- Physica B: Condensed Matter, Vol. 186-188
5 f -Shell correlation effects in dioxides of light actinides studied by O 1 s x-ray absorption and emission spectroscopies and first-principles calculations
journal, July 2015
- Modin, A.; Suzuki, M-T; Vegelius, J.
- Journal of Physics: Condensed Matter, Vol. 27, Issue 31
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
Electronic structure and ionicity of actinide oxides from first principles
journal, January 2010
- Petit, L.; Svane, A.; Szotek, Z.
- Physical Review B, Vol. 81, Issue 4
Electronic correlation and transport properties of nuclear fuel materials
journal, November 2011
- Yin, Quan; Kutepov, Andrey; Haule, Kristjan
- Physical Review B, Vol. 84, Issue 19
Dispersion in the Mott insulator UO 2 : A comparison of photoemission spectroscopy and screened hybrid density functional theory
journal, October 2008
- Roy, Lindsay E.; Durakiewicz, Tomasz; Martin, Richard L.
- Journal of Computational Chemistry, Vol. 29, Issue 13
Chemical State of Complex Uranium Oxides
journal, December 2013
- Kvashnina, K. O.; Butorin, S. M.; Martin, P.
- Physical Review Letters, Vol. 111, Issue 25
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
High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds
journal, July 2016
- Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 29
Crystal-Field and Covalency Effects in Uranates: An X-ray Spectroscopic Study
journal, June 2016
- Butorin, Sergei M.; Kvashnina, Kristina O.; Smith, Anna L.
- Chemistry - A European Journal, Vol. 22, Issue 28
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
Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides
journal, March 2016
- Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.
- Analytical Chemistry, Vol. 88, Issue 8
The electron spectrum of UF 6 recorded in the gas phase
journal, June 1984
- Mårtensson, N.; Malmquist, P. ‐Å.; Svensson, S.
- The Journal of Chemical Physics, Vol. 80, Issue 11
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
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
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
Localized Magnetic States in Metals
journal, October 1961
- Anderson, P. W.
- Physical Review, Vol. 124, Issue 1
The Theory of Complex Spectra
journal, November 1929
- Slater, J. C.
- Physical Review, Vol. 34, Issue 10
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
Calculation of magnetic x-ray dichroism in 4 d and 5 d absorption spectra of actinides
journal, August 1991
- Ogasawara, H.; Kotani, A.; Thole, B. T.
- Physical Review B, Vol. 44, Issue 5
Nature of the states in actinide metals
journal, February 2009
- Moore, Kevin T.; van der Laan, Gerrit
- Reviews of Modern Physics, Vol. 81, Issue 1
Resonant Inelastic Soft X-Ray Scattering Spectroscopy of Light-Actinide Materials
book, January 2011
- Butorin, Sergei M.
- Actinide Nanoparticle Research
Speciation of Uranium After Microbial Action by XANES and XPS
journal, January 1993
- Dodge, Cleveland J.; Francis, A. J.; Lu, F.
- MRS Proceedings, Vol. 307
Resonant X-Ray Emission Spectroscopy in Dy Compounds
journal, July 1994
- Tanaka, Satoshi; Okada, Kozo; Kotani, Akio
- Journal of the Physical Society of Japan, Vol. 63, Issue 7
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
Configuration dependence of hopping matrix elements in the Anderson model
journal, August 1988
- Gunnarsson, O.; Jepsen, O.
- Physical Review B, Vol. 38, Issue 5
Theoretical modeling of the uranium 4f XPS for U(VI) and U(IV) oxides
journal, December 2013
- Bagus, Paul S.; Nelin, Connie J.; Ilton, Eugene S.
- The Journal of Chemical Physics, Vol. 139, Issue 24
Crystal fields in UO 2 - revisited
journal, November 2010
- Nakotte, H.; Rajaram, R.; Kern, S.
- Journal of Physics: Conference Series, Vol. 251
Core electron excitations in U 4+ : modelling of the nd 10 5f 2 → nd 9 5f 3 transitions with n = 3, 4 and 5 by ligand field tools and density functional theory
journal, January 2016
- Ramanantoanina, Harry; Kuri, Goutam; Daul, Claude
- Physical Chemistry Chemical Physics, Vol. 18, Issue 28
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
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
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
Works referencing / citing this record:
A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO 2 Nanoparticles
journal, December 2019
- Kvashnina, Kristina O.; Romanchuk, Anna Yu.; Pidchenko, Ivan
- Angewandte Chemie International Edition, Vol. 58, Issue 49
A Novel Metastable Pentavalent Plutonium Solid Phase on the Pathway from Aqueous Plutonium(VI) to PuO 2 Nanoparticles
journal, October 2019
- Kvashnina, Kristina O.; Romanchuk, Anna Yu.; Pidchenko, Ivan
- Angewandte Chemie, Vol. 131, Issue 49
Figures / Tables found in this record: