Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.; Suzuki, Michi-To; Oppeneer, Peter M.; Andersson, David A.; Shuh, David K.

doi:10.1021/acs.analchem.5b04380

Title: Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

Abstract

A systematic X-ray absorption study at actinide N_6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO₂, PuO₂, and UO₃. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L_2,3 (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N_6,7 spectral shape to changes in the compound crystal structure. Finally, for nonstoichiometric NpO_2-x, the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO₂ which is in agreement with the tentative Np-O phase diagram.

Authors:

Butorin, Sergei M. ^[1]; Modin, Anders ^[1]; Vegelius, Johan R. ^[1]; Suzuki, Michi-To ^[2]; Oppeneer, Peter M. ^[1]; Andersson, David A. ^[3]; Shuh, David K. ^[4]

Uppsala Univ. (Sweden). Dept. of Physics and Astronomy
Uppsala Univ. (Sweden). Dept. of Physics and Astronomy; RIKEN, Saitama (Japan). Center for Emergent Matter Science
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Publication Date:: Wed Mar 23 00:00:00 EDT 2016

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Swedish Research Council (SRC); Swedish National Infrastructure for Computing (SNIC); European Atomic Energy Community

OSTI Identifier:: 1436135

Grant/Contract Number:: AC02-05CH11231; 269903

Resource Type:: Accepted Manuscript

Journal Name:: Analytical Chemistry

Additional Journal Information:: Journal Volume: 88; Journal Issue: 8; Journal ID: ISSN 0003-2700

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Suzuki, Michi-To, Oppeneer, Peter M., Andersson, David A., and Shuh, David K. Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides.  United States: N. p., 2016. 
Web.  doi:10.1021/acs.analchem.5b04380.

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                    Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Suzuki, Michi-To, Oppeneer, Peter M., Andersson, David A., & Shuh, David K. Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides.  United States.  https://doi.org/10.1021/acs.analchem.5b04380

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                    Butorin, Sergei M., Modin, Anders, Vegelius, Johan R., Suzuki, Michi-To, Oppeneer, Peter M., Andersson, David A., and Shuh, David K. Wed .  
"Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides".  United States.  https://doi.org/10.1021/acs.analchem.5b04380.  https://www.osti.gov/servlets/purl/1436135.

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@article{osti_1436135,

  title        = {Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides},

  author       = {Butorin, Sergei M. and Modin, Anders and Vegelius, Johan R. and Suzuki, Michi-To and Oppeneer, Peter M. and Andersson, David A. and Shuh, David K.},

  abstractNote = {A systematic X-ray absorption study at actinide N6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO2, PuO2, and UO3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L2,3 (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N6,7 spectral shape to changes in the compound crystal structure. Finally, for nonstoichiometric NpO2-x, the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO2 which is in agreement with the tentative Np-O phase diagram.},

  doi          = {10.1021/acs.analchem.5b04380},

  journal      = {Analytical Chemistry},

  number       = 8,

  volume       = 88,

  place        = {United States},

  year         = {Wed Mar 23 00:00:00 EDT 2016},

  month        = {Wed Mar 23 00:00:00 EDT 2016}

}

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Works referencing / citing this record:

Study of electronic structure in the L-edge spectroscopy of actinide materials: UO ₂ as an example
journal, January 2019

Ramanantoanina, Harry; Kuri, Goutam; Martin, Matthias
Physical Chemistry Chemical Physics, Vol. 21, Issue 15
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Theoretical insight into the magnetic circular dichroism of uranium N _6,7 ‐edge X‐ray absorption
journal, October 2019

Ramanantoanina, Harry; Gruden, Maja
International Journal of Quantum Chemistry, Vol. 120, Issue 3
DOI: 10.1002/qua.26081

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Title: Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

Abstract

Citation Formats

Widths of the Atomic k–n7 Levels journal, January 2001

High energy resolution x-ray absorption spectroscopy study of uranium in varying valence states journal, December 2010

Role of resonant inelastic X-ray scattering in high-resolution core-level spectroscopy of actinide materials journal, June 2014

The electron spectrum of UF 6 recorded in the gas phase journal, June 1984

Core-level lifetimes as determined by x-ray photoelectron spectroscopy measurements journal, October 1980

Characterization of f electrons in light lanthanide and actinide metals by electron-energy-loss and x-ray photoelectron spectroscopy journal, March 1984

Orbital Specificity in the Unoccupied States of UO 2 from Resonant Inverse Photoelectron Spectroscopy journal, October 2011

f - f origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations journal, April 2011

Phase relationships in the neptunium-oxygen system journal, May 1987

Photoelectron spectroscopy (UPS/XPS) study of Np2O3 formation on the surface of neptunium metal journal, December 1987

Reaction of neptunium with molecular and atomic oxygen: Formation and stability of surface oxides journal, June 2009

Actinide transmutation: new investigation on some actinide compounds journal, June 1998

Chemical State of Complex Uranium Oxides journal, December 2013

Performance of a high resolution, high flux density SGM undulator beamline at the ALS (invited) journal, February 1995

Resonant Inelastic Soft X-Ray Scattering Spectroscopy of Light-Actinide Materials book, January 2011

Chemical Reduction of Actinides Probed by Resonant Inelastic X-ray Scattering journal, November 2013

First-principles theory of multipolar order in neptunium dioxide journal, December 2010

Microscopic theory of the insulating electronic ground states of the actinide dioxides AnO 2 (An = U, Np, Pu, Am, and Cm) journal, November 2013

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

Determination of the Insulation Gap of Uranium Oxides by Spectroscopic Ellipsometry and Density Functional Theory journal, August 2013

On the Photoabsorption Cross Section of Uranium Metal journal, October 1985

Surface reactions of uranium oxide powder, thin films and single crystals journal, March 2010

X-ray photoelectron-spectroscopy study of oxides of the transuranium elements Np, Pu, Am, Cm, Bk, and Cf journal, March 1977

Sensitivity to Actinide Doping of Uranium Compounds by Resonant Inelastic X-ray Scattering at Uranium L 3 Edge journal, August 2015

Indication of single-crystal PuO 2 oxidation from O 1 s x-ray absorption spectra journal, February 2011

Pentavalent Uranium Oxide via Reduction of [UO 2 ] 2+ Under Hydrothermal Reaction Conditions † journal, November 2008

Neutron powder profile studies of the gamma uranium trioxide phases journal, January 1977

Study of electronic structure in the L-edge spectroscopy of actinide materials: UO 2 as an example journal, January 2019

Theoretical insight into the magnetic circular dichroism of uranium N 6,7 ‐edge X‐ray absorption journal, October 2019

Widths of the Atomic k–n7 Levels
journal, January 2001

High energy resolution x-ray absorption spectroscopy study of uranium in varying valence states
journal, December 2010

Role of resonant inelastic X-ray scattering in high-resolution core-level spectroscopy of actinide materials
journal, June 2014

The electron spectrum of UF ₆ recorded in the gas phase
journal, June 1984

Core-level lifetimes as determined by x-ray photoelectron spectroscopy measurements
journal, October 1980

Characterization of $f$ electrons in light lanthanide and actinide metals by electron-energy-loss and x-ray photoelectron spectroscopy
journal, March 1984

Orbital Specificity in the Unoccupied States of ${UO}_{2}$ from Resonant Inverse Photoelectron Spectroscopy
journal, October 2011

$f$ - $f$ origin of the insulating state in uranium dioxide: X-ray absorption experiments and first-principles calculations
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Phase relationships in the neptunium-oxygen system
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Photoelectron spectroscopy (UPS/XPS) study of Np2O3 formation on the surface of neptunium metal
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Reaction of neptunium with molecular and atomic oxygen: Formation and stability of surface oxides
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Chemical State of Complex Uranium Oxides
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Resonant Inelastic Soft X-Ray Scattering Spectroscopy of Light-Actinide Materials
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First-principles theory of multipolar order in neptunium dioxide
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