The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

doi:https://doi.org/10.1016/j.elspec.2014.01.020

Title: The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

Abstract

X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causes will be discussed.

Authors:

Tobin, J. G. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Publication Date:: 2013-05-03

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1237532

Report Number(s):: LLNL-JRNL-636485
Journal ID: ISSN 0368-2048

Grant/Contract Number:: AC52-07NA27344

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Electron Spectroscopy and Related Phenomena

Additional Journal Information:: Journal Volume: 194; Journal ID: ISSN 0368-2048

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; actinides; photoelectron spectroscopy; x-ray absorption spectroscopy

Citation Formats


                    Tobin, J. G. The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds.  United States: N. p., 2013. 
        Web.  doi:10.1016/j.elspec.2014.01.020.

Copy to clipboard


                    Tobin, J. G. The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds.  United States.  https://doi.org/10.1016/j.elspec.2014.01.020

Copy to clipboard


                    Tobin, J. G. Fri .  
        "The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds".  United States.  https://doi.org/10.1016/j.elspec.2014.01.020.  https://www.osti.gov/servlets/purl/1237532.

Copy to clipboard


                    
@article{osti_1237532,

  title        = {The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds},

  author       = {Tobin, J. G.},

  abstractNote = {X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causes will be discussed.},

  doi          = {10.1016/j.elspec.2014.01.020},

  url          = {https://www.osti.gov/biblio/1237532},
  journal      = {Journal of Electron Spectroscopy and Related Phenomena},

  issn         = {0368-2048},

  number       = ,

  volume       = 194,

  place        = {United States},

  year         = {2013},

  month        = {5}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.elspec.2014.01.020

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

Covalency in oxidized uranium
journal, July 2015

Tobin, J. G.; Yu, S. -W.; Qiao, R.
Physical Review B, Vol. 92, Issue 4
https://doi.org/10.1103/physrevb.92.045130

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
https://doi.org/10.1103/physrevb.92.035111

The Issue of Pu 5f Occupation
journal, January 2018

Tobin, J. G.
MRS Advances, Vol. 3, Issue 53
https://doi.org/10.1557/adv.2018.372

Similar records in OSTI.GOV collections:

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

Journal Article Butorin, Sergei M. ; Kvashnina, Kristina O. ; Vegelius, Johan R. ; ... - Proceedings of the National Academy of Sciences of the United States of America

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 statemore »« less
Cited by 11
https://doi.org/10.1073/pnas.1601741113

Full Text Available
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 Article Kozimor, Stosh A ; Yang, Ping ; Batista, Enrique R ; ... - Journal of the American Chemical Society, 131(34):12125-12136

We describe the use of Cl K-edge X-ray Absorption Spectroscopy (XAS) and both ground state and time-dependent hybrid density functional theory (DFT) to probe electronic structure and determine the degree of orbital mixing in M-Cl bonds for (C5Me5)2MCl2 (M = Ti, 1; Zr, 2; Hf, 3; Th, 4; and U, 5), where we can directly compare a class of structurally similar compounds for d- and f-elements. We report direct experimental evidence for covalency in M-Cl bonding, including actinides, and offer insight into the relative roles of the valence f- and dorbitals in these systems. The Cl K-edge XAS data formore »« less
https://doi.org/10.1021/ja9015759
Probing the population of the spin-orbit split levels in the actinide 5f states

Journal Article Moore, K ; der Laan, G v ; Tobin, J ; ... - Ultramicroscopy

Spin-orbit interaction in the 5f states is believed to strongly influence exotic behaviors observed in actinides metals and compounds. Understanding these interactions and how they relate to the actinide series is of considerable importance. To address this issue, the branching ratio of the white-line peaks of the N4,5 edges for the light actinide metals, {alpha}-Th, {alpha}-U, and {alpha}-Pu were recorded using electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM) and synchrotron-radiation-based x-ray absorption spectroscopy (XAS). Using the spin-orbit sum rule and the branching ratios from both experimental spectra and many-electron atomic spectral calculations, accurate values of the spin-orbitmore »« less
Full Text Available
Investigation of the Unoccupied Electronic Structure of UO2 with Bermstrahlung Isochromat Spectroscopy and X-Ray Absorption Spectroscopy

Conference Tobin, J G ; Yu, S W ; Crowhurst, J C ; ...

UO{sub 2} is an important nuclear fuel for electrical power generation. Global goal : Actinides (5f electron systems) exhibit fascinating physical and chemical properties, due to 5f electron correlation, including the highly radioactive systems such as Pu. Onsite Instrumentation: A spectroscopic system containing spin resolved photoelectron spectroscopy (SRPES) and bremsstrahlung isochromat spectroscopy (BIS) has been built and commissioned at LLNL. ALS Instrumentation: The XAS was done on Beamline 8. Both Total Electron Yield (TEY) and Total Fluorescence Yield (TFY) were used. TFY is less surface sensitive than TEY. A combined experimental and theoretical study of Uranium Dioxide has been performed,more »« less
Full Text Available
Final Technical Report

Technical Report Ray, Asok K

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compoundsmore »« less
https://doi.org/10.2172/1040790

Full Text Available

Similar Records

Title: The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

Abstract

Citation Formats

Covalency in oxidized uranium journal, July 2015

Oxidation and crystal field effects in uranium journal, July 2015

The Issue of Pu 5f Occupation journal, January 2018

Covalency in oxidized uranium
journal, July 2015

Oxidation and crystal field effects in uranium
journal, July 2015

The Issue of Pu 5f Occupation
journal, January 2018