Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects
Abstract
Experimental oxygen K-edge spectra of ThO2 and CeO2 are presented and interpreted based on density functional theory (DFT). The contribution of d and f orbitals to the O K-edge spectrum is identified as well-distinguished peaks, the presence of which evidences the strong hybridization of Th and Ce metal centers with O orbitals. The sensitivity of the O K-edge to both f- and d-states in the absence of a core–hole on the metal ion results in an insightful overview of the electronic structure involved in the chemical bond. In particular, the large bandwidth of the Th 5f band as compared to the Ce 4f band is observed as a set of wider and more substantial set of peaks in the O K-edge, confirming the stronger hybridization of the former with O orbitals. The peak ascribed to the 5f band of ThO2 is found at higher energy than the 6d band, as predicted from DFT calculations on actinide dioxides. Here, to highlight the sensitivity and the potential use of the O K-edge for the characterization of ThO2-based systems, the sensitivity of the spectrum to structural changes such as lattice expansion and size reduction are calculated and discussed.
- Authors:
-
[1];
[2];
[3];
[4];
[5];
[5];
[1]
- European Synchrotron Radiation Facility (ESRF), Grenoble (France); Helmholtz-Zentrum Dresden-Rossendorf (Germany)
- Univ. Montpellier (France)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Uppsala Univ. (Sweden)
- European Synchrotron Radiation Facility (ESRF), Grenoble (France)
- 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 & Biosciences Division; European Research Council (ERC); Swedish Research Council (SRC)
- OSTI Identifier:
- 1969344
- Grant/Contract Number:
- AC02-05CH11231; 759696; 2017-06465
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 127; Journal Issue: 6; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; absorption; actinides; energy; nanoparticles; x-ray absorption near edge spectroscopy
Citation Formats
Amidani, Lucia, Dumas, Thomas, Shuh, David K., Butorin, Sergei M., Sahle, Christoph J., Longo, Alessandro, and Kvashnina, Kristina O. Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects. United States: N. p., 2023.
Web. doi:10.1021/acs.jpcc.2c07771.
Amidani, Lucia, Dumas, Thomas, Shuh, David K., Butorin, Sergei M., Sahle, Christoph J., Longo, Alessandro, & Kvashnina, Kristina O. Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects. United States. https://doi.org/10.1021/acs.jpcc.2c07771
Amidani, Lucia, Dumas, Thomas, Shuh, David K., Butorin, Sergei M., Sahle, Christoph J., Longo, Alessandro, and Kvashnina, Kristina O. Wed .
"Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects". United States. https://doi.org/10.1021/acs.jpcc.2c07771. https://www.osti.gov/servlets/purl/1969344.
@article{osti_1969344,
title = {Oxygen K-Edge X-ray Absorption Spectra of ThO2 and CeO2: Experiment, Interpretation, and Structural Effects},
author = {Amidani, Lucia and Dumas, Thomas and Shuh, David K. and Butorin, Sergei M. and Sahle, Christoph J. and Longo, Alessandro and Kvashnina, Kristina O.},
abstractNote = {Experimental oxygen K-edge spectra of ThO2 and CeO2 are presented and interpreted based on density functional theory (DFT). The contribution of d and f orbitals to the O K-edge spectrum is identified as well-distinguished peaks, the presence of which evidences the strong hybridization of Th and Ce metal centers with O orbitals. The sensitivity of the O K-edge to both f- and d-states in the absence of a core–hole on the metal ion results in an insightful overview of the electronic structure involved in the chemical bond. In particular, the large bandwidth of the Th 5f band as compared to the Ce 4f band is observed as a set of wider and more substantial set of peaks in the O K-edge, confirming the stronger hybridization of the former with O orbitals. The peak ascribed to the 5f band of ThO2 is found at higher energy than the 6d band, as predicted from DFT calculations on actinide dioxides. Here, to highlight the sensitivity and the potential use of the O K-edge for the characterization of ThO2-based systems, the sensitivity of the spectrum to structural changes such as lattice expansion and size reduction are calculated and discussed.},
doi = {10.1021/acs.jpcc.2c07771},
journal = {Journal of Physical Chemistry. C},
number = 6,
volume = 127,
place = {United States},
year = {Wed Feb 08 00:00:00 EST 2023},
month = {Wed Feb 08 00:00:00 EST 2023}
}
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Works referenced in this record:
X-ray absorption at the oxygen K edge in cubic f oxides examined using a full multiple-scattering approach
journal, September 1999
- Wu, Z. Y.; Jollet, F.; Gota, S.
- Journal of Physics: Condensed Matter, Vol. 11, Issue 37
Separate measurement of the 5f5/2 and 5f7/2 unoccupied density of states of UO2
journal, April 2019
- Tobin, J. G.; Nowak, S.; Booth, C. H.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 232
Covalent interactions in oxides
journal, June 2014
- Bagus, Paul S.; Nelin, Connie J.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
Covalency in Actinide Compounds
journal, January 2021
- Pace, Kristen A.; Klepov, Vladislav V.; Berseneva, Anna A.
- Chemistry – A European Journal, Vol. 27, Issue 19
Structural properties of ultra-small thorium and uranium dioxide nanoparticles embedded in a covalent organic framework
journal, January 2020
- Moreau, Liane M.; Herve, Alexandre; Straub, Mark D.
- Chemical Science, Vol. 11, Issue 18
From X-ray Amorphous ThO2 to Crystalline Nanoparticles through Long-Term Aging at Room Temperature
journal, December 2022
- Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Seregina, Irina F.
- The Journal of Physical Chemistry C, Vol. 127, Issue 1
Transuranium compounds probed by nonresonant inelastic x-ray scattering
journal, February 2020
- Sundermann, M.; Simonelli, L.; Huotari, S.
- Physical Review B, Vol. 101, Issue 7
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 – Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
journal, March 2012
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 134, Issue 12
Speciation Change of Uranyl in Lithium Borate Glasses
journal, April 2019
- Hunault, Myrtille O. J. Y.; Lelong, Gérald; Cormier, Laurent
- Inorganic Chemistry, Vol. 58, Issue 10
Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO 2 , PrO 2 , and TbO 2
journal, November 2017
- Minasian, Stefan G.; Batista, Enrique R.; Booth, Corwin H.
- Journal of the American Chemical Society, Vol. 139, Issue 49
Synthesis of new mixed actinides oxalates as precursors of actinides oxide solid solutions
journal, October 2007
- Arab-Chapelet, B.; Grandjean, S.; Nowogrocki, G.
- Journal of Alloys and Compounds, Vol. 444-445
Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory
journal, January 2013
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 135, Issue 5
Indication of single-crystal PuO oxidation from O 1 x-ray absorption spectra
journal, February 2011
- Modin, A.; Yun, Y.; Suzuki, M. -T.
- Physical Review B, Vol. 83, Issue 7
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
Local Structure of Actinide Dioxide Solid Solutions Th 1 - x U x O 2 and Th 1 - x Pu x O 2
journal, May 2006
- Hubert, S.; Purans, J.; Heisbourg, G.
- Inorganic Chemistry, Vol. 45, Issue 10
Polarization Dependent High Energy Resolution X-ray Absorption Study of Dicesium Uranyl Tetrachloride
journal, December 2014
- Vitova, Tonya; Green, Jennifer C.; Denning, Robert G.
- Inorganic Chemistry, Vol. 54, Issue 1
Covalency in f-element complexes
journal, January 2013
- Neidig, Michael L.; Clark, David L.; Martin, Richard L.
- Coordination Chemistry Reviews, Vol. 257, Issue 2
Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids
journal, March 2017
- Dalodière, Elodie; Virot, Matthieu; Morosini, Vincent
- Scientific Reports, Vol. 7, Issue 1
Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010
- Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 21
Quantification of f-element covalency through analysis of the electron density: insights from simulation
journal, January 2017
- Kerridge, A.
- Chemical Communications, Vol. 53, Issue 50
Theory of X-Ray Raman Scattering
journal, February 1967
- Mizuno, Yukio; Ohmura, Yoshihiro
- Journal of the Physical Society of Japan, Vol. 22, Issue 2
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
Uranium electric-multipole transitions probed by nonresonant inelastic x-ray scattering
journal, May 2010
- Caciuffo, R.; van der Laan, G.; Simonelli, L.
- Physical Review B, Vol. 81, Issue 19
Mechanical and electronic properties of , , and alloys
journal, July 2009
- Sevik, C.; Çağın, T.
- Physical Review B, Vol. 80, Issue 1
Time-dependent density functional theory applied to x-ray absorption spectroscopy
journal, April 2012
- Bunău, Oana; Joly, Yves
- Physical Review B, Vol. 85, Issue 15
Dehydration of the Uranyl Peroxide Studtite, [UO 2 (η 2 -O 2 )(H 2 O) 2 ]·2H 2 O, Affords a Drastic Change in the Electronic Structure: A Combined X-ray Spectroscopic and Theoretical Analysis
journal, February 2018
- Vitova, Tonya; Pidchenko, Ivan; Biswas, Saptarshi
- Inorganic Chemistry, Vol. 57, Issue 4
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl 6 x – ( x = 3, 2)
journal, February 2015
- Löble, Matthias W.; Keith, Jason M.; Altman, Alison B.
- Journal of the American Chemical Society, Vol. 137, Issue 7
Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
journal, September 2009
- Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 131, Issue 34
Full-Potential Simulation of X-ray Raman Scattering Spectroscopy
journal, April 2017
- Joly, Yves; Cavallari, Chiara; Guda, Sergey A.
- Journal of Chemical Theory and Computation, Vol. 13, Issue 5
Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry
journal, January 2010
- Fillaux, Clara; Guillaumont, Dominique; Berthet, Jean-Claude
- Physical Chemistry Chemical Physics, Vol. 12, Issue 42
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
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory
journal, July 2007
- Prodan, Ionut D.; Scuseria, Gustavo E.; Martin, Richard L.
- Physical Review B, Vol. 76, Issue 3
Nanoscale oxygen defect gradients in UO 2+ x surfaces
journal, August 2019
- Spurgeon, Steven R.; Sassi, Michel; Ophus, Colin
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 35
The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study
journal, January 2016
- Lukens, W. W.; Speldrich, M.; Yang, P.
- Dalton Transactions, Vol. 45, Issue 28
Crystal-field states of probed by directional dependence of nonresonant inelastic x-ray scattering
journal, November 2018
- Sundermann, M.; van der Laan, G.; Severing, A.
- Physical Review B, Vol. 98, Issue 20
Size Effects in Nanocrystalline Thoria
journal, August 2019
- Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Likhosherstova, Daria V.
- The Journal of Physical Chemistry C, Vol. 123, Issue 37
From antiferromagnetic and hidden order to Pauli paramagnetism in U M 2 Si 2 compounds with 5 f electron duality
journal, November 2020
- Amorese, Andrea; Sundermann, Martin; Leedahl, Brett
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 48
Self-consistent aspects of x-ray absorption calculations
journal, August 2009
- Bunău, O.; Joly, Y.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 34
Computational and Spectroscopic Tools for the Detection of Bond Covalency in Pu(IV) Materials
journal, October 2021
- Bagus, Paul S.; Schacherl, Bianca; Vitova, Tonya
- Inorganic Chemistry, Vol. 60, Issue 21
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
Probing the Local Coordination of Hexavalent Uranium and the Splitting of 5f Orbitals Induced by Chemical Bonding
journal, October 2021
- Amidani, Lucia; Retegan, Marius; Volkova, Anna
- Inorganic Chemistry, Vol. 60, Issue 21
Thorium amidates function as single-source molecular precursors for thorium dioxide
journal, January 2021
- Straub, Mark D.; Ouellette, Erik T.; Boreen, Michael A.
- Chemical Communications, Vol. 57, Issue 40
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
Understanding the size effects on the electronic structure of ThO 2 nanoparticles
journal, January 2019
- Amidani, Lucia; Plakhova, Tatiana V.; Romanchuk, Anna Yu.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 20
Crystal Orbital Overlap Population and X-ray Absorption Spectroscopy
journal, June 2020
- Diaz-Lopez, Maria; Guda, Sergey A.; Joly, Yves
- The Journal of Physical Chemistry A, Vol. 124, Issue 29
Chemical State of Complex Uranium Oxides
journal, December 2013
- Kvashnina, K. O.; Butorin, S. M.; Martin, P.
- Physical Review Letters, Vol. 111, Issue 25
Planning, performing and analyzing X-ray Raman scattering experiments
journal, February 2015
- Sahle, Ch. J.; Mirone, A.; Niskanen, J.
- Journal of Synchrotron Radiation, Vol. 22, Issue 2
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
The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory
journal, January 2016
- Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara
- Physical Chemistry Chemical Physics, Vol. 18, Issue 4
Emergence of the structure-directing role of f-orbital overlap-driven covalency
journal, February 2019
- Lu, Erli; Sajjad, Saira; Berryman, Victoria E. J.
- Nature Communications, Vol. 10, Issue 1
Evolution of the Uranium Chemical State in Mixed-Valence Oxides
journal, May 2017
- Leinders, Gregory; Bes, René; Pakarinen, Janne
- Inorganic Chemistry, Vol. 56, Issue 12
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
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
journal, January 2005
- Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O.
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
The Renaissance of Non-Aqueous Uranium Chemistry
journal, June 2015
- Liddle, Stephen T.
- Angewandte Chemie International Edition, Vol. 54, Issue 30
Alkali Uranyl Borates: Bond Length, Equatorial Coordination and 5f States
journal, January 2021
- Hunault, Myrtille O. J. Y.; Menut, Denis; Tougait, Olivier
- Crystals, Vol. 11, Issue 1
The electronic structure of f-element Prussian blue analogs determined by soft X-ray absorption spectroscopy
journal, January 2018
- Dumas, Thomas; Guillaumont, Dominique; Moisy, Philippe
- Chemical Communications, Vol. 54, Issue 86
Synthesis and characterization of mixed An(IV)An(III) oxalates (An(IV)=Th, Np, U or Pu and An(III)=Pu or Am)
journal, February 2008
- Arab-Chapelet, B.; Grandjean, S.; Nowogrocki, G.
- Journal of Nuclear Materials, Vol. 373, Issue 1-3
Determination of Ce4+/Ce3+ in electron-beam-damaged CeO2 by electron energy-loss spectroscopy
journal, December 1999
- Garvie, L. A. J.; Buseck, P. R.
- Journal of Physics and Chemistry of Solids, Vol. 60, Issue 12
Experimental and Theoretical Comparison of the O K-Edge Nonresonant Inelastic X-ray Scattering and X-ray Absorption Spectra of NaReO 4
journal, October 2010
- Bradley, Joseph A.; Yang, Ping; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 132, Issue 39
Energy-Degeneracy-Driven Covalency in Actinide Bonding
journal, December 2018
- Su, Jing; Batista, Enrique R.; Boland, Kevin S.
- Journal of the American Chemical Society, Vol. 140, Issue 51
Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007
- Denning, Robert G.
- The Journal of Physical Chemistry A, Vol. 111, Issue 20
High-energy resolution X-ray spectroscopy at actinide M4,5 and ligand K edges: what we know, what we want to know, and what we can know
journal, January 2022
- Kvashnina, Kristina O.; Butorin, Sergei M.
- Chemical Communications, Vol. 58, Issue 3
Covalency in actinide(iv ) hexachlorides in relation to the chlorine K-edge X-ray absorption structure
journal, January 2022
- Sergentu, Dumitru-Claudiu; Autschbach, Jochen
- Chemical Science, Vol. 13, Issue 11
The Application of HEXS and HERFD XANES for Accurate Structural Characterisation of Actinide Nanomaterials: The Case of ThO 2
journal, November 2020
- Amidani, Lucia; Vaughan, Gavin B. M.; Plakhova, Tatiana V.
- Chemistry – A European Journal, Vol. 27, Issue 1
The missing pieces of the PuO 2 nanoparticle puzzle
journal, January 2020
- Gerber, Evgeny; Romanchuk, Anna Yu.; Pidchenko, Ivan
- Nanoscale, Vol. 12, Issue 35
Oxygen K-edge X-ray Absorption Spectra
journal, April 2020
- Frati, Federica; Hunault, Myrtille O. J. Y.; de Groot, Frank M. F.
- Chemical Reviews, Vol. 120, Issue 9
Density Functional Theory Studies of the Electronic Structure of Solid State Actinide Oxides
journal, October 2012
- Wen, Xiao-Dong; Martin, Richard L.; Henderson, Thomas M.
- Chemical Reviews, Vol. 113, Issue 2
A large-solid-angle X-ray Raman scattering spectrometer at ID20 of the European Synchrotron Radiation Facility
journal, February 2017
- Huotari, S.; Sahle, Ch. J.; Henriquet, Ch.
- Journal of Synchrotron Radiation, Vol. 24, Issue 2