Towards the Quantification of 5f Delocalization

Tobin, J. G.; Nowak, S.; Yu, S. -W.; Alonso-Mori, R.; Kroll, T.; Nordlund, D.; Weng, T. -C.; Sokaras, D.

doi:10.3390/app10082918

Towards the Quantification of 5f Delocalization

Journal Article · Thu Apr 23 00:00:00 EDT 2020 · Applied Sciences

DOI:https://doi.org/10.3390/app10082918· OSTI ID:2377886

; Nowak, S.; Yu, S. -W.; Alonso-Mori, R.; Kroll, T.; Nordlund, D.; Weng, T. -C.; Sokaras, D.

By using M4,5 X-ray Emission Spectroscopy (XES) in the tender X-ray regime, it is possible to quantify 5f delocalization in the actinides. Previous analyses, utilizing the Branching Ratio (BR) in the N4,5 X-ray Absorption Spectroscopy (XAS), could not discriminate between the cases of localized n = 2 and delocalized n = 3, in uranium materials, where n is the number of 5f electrons on the U entity. Here, it is shown that, by employing the ubiquitous 6p → 3d XES as a point of normalization, the localized n = 2 and delocalized n = 3 cases can be easily distinguished and quantified.

View Journal Article

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC52-07NA27344

OSTI ID:: 2377886

Alternate ID(s):: OSTI ID: 1616165
OSTI ID: 1682521

Report Number(s):: LLNL-JRNL--811150; PII: app10082918

Journal Information:: Applied Sciences, Journal Name: Applied Sciences Journal Issue: 8 Vol. 10; ISSN ASPCC7; ISSN 2076-3417

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

References (39)

Probing actinide electronic structure through pu cluster calculations Ryzhkov, Mickhail V.; Mirmelstein, Alexei; Yu, Sung-Woo International Journal of Quantum Chemistry, Vol. 113, Issue 16 https://doi.org/10.1002/qua.24417	journal	February 2013
Metallic radii and electron configurations of the 5f−6d metals Zachariasen, W. H. Journal of Inorganic and Nuclear Chemistry, Vol. 35, Issue 10 https://doi.org/10.1016/0022-1902(73)80357-4	journal	October 1973
Electronic structure and Coulomb correlation energy in UO2 single crystal Baer, Y.; Schoenes, J. Solid State Communications, Vol. 33, Issue 8 https://doi.org/10.1016/0038-1098(80)91210-7	journal	February 1980
Inverse photoemission study of uranium dioxide Chauvet, G.; Baptist, R. Solid State Communications, Vol. 43, Issue 11 https://doi.org/10.1016/0038-1098(82)90841-9	journal	September 1982
Bonding in uranium oxides: The role of 5f electrons Veal, B. W.; Lam, D. J. Physics Letters A, Vol. 49, Issue 6 https://doi.org/10.1016/0375-9601(74)90318-1	journal	October 1974
Multi-electronic effects in uranium dioxide from X-ray Emission Spectroscopy Yu, S. -W.; Tobin, J. G. Journal of Electron Spectroscopy and Related Phenomena, Vol. 187 https://doi.org/10.1016/j.elspec.2013.02.007	journal	April 2013
The effects of mesoscale confinement in Pu clusters and isolated particles Ryzhkov, M. V.; Mirmelstein, A.; Delley, B. Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2013.11.015	journal	June 2014
The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds Tobin, J. G. Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2014.01.020	journal	June 2014
Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy Booth, C. H.; Medling, S. A.; Jiang, Yu Journal of Electron Spectroscopy and Related Phenomena, Vol. 194 https://doi.org/10.1016/j.elspec.2014.03.004	journal	June 2014
Electron spectroscopy of the oxidation and aging of U and Pu Tobin, J. G.; Shuh, D. K. Journal of Electron Spectroscopy and Related Phenomena, Vol. 205 https://doi.org/10.1016/j.elspec.2015.09.001	journal	November 2015
Separate measurement of the 5f5/2 and 5f7/2 unoccupied density of states of UO2 Tobin, J. G.; Nowak, S.; Booth, C. H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 232 https://doi.org/10.1016/j.elspec.2019.03.003	journal	April 2019
Beyond spin-orbit: Probing electron correlation in the Pu 5f states using spin-resolved photoelectron spectroscopy Tobin, J. G. Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.107	journal	October 2007
The role of the 5f valence orbitals of early actinides in chemical bonding Vitova, T.; Pidchenko, I.; Fellhauer, D. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms16053	journal	July 2017
A versatile Johansson-type tender x-ray emission spectrometer Nowak, S. H.; Armenta, R.; Schwartz, C. P. Review of Scientific Instruments, Vol. 91, Issue 3 https://doi.org/10.1063/1.5121853	journal	March 2020
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics Booth, C. H.; Jiang, Y.; Wang, D. L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 26 https://doi.org/10.1073/pnas.1200725109	journal	June 2012
Band structures of 4 f and 5 f materials studied by angle-resolved photoelectron spectroscopy Fujimori, Shin-ichi Journal of Physics: Condensed Matter, Vol. 28, Issue 15 https://doi.org/10.1088/0953-8984/28/15/153002	journal	March 2016
Observation of 5f intermediate coupling in uranium x-ray emission spectroscopy Tobin, J. G.; Nowak, S.; Yu, S-W Journal of Physics Communications, Vol. 4, Issue 1 https://doi.org/10.1088/2399-6528/ab6940	journal	January 2020
X-ray photoelectron studies of thorium, uranium, and their dioxides Veal, B. W.; Lam, D. J. Physical Review B, Vol. 10, Issue 12 https://doi.org/10.1103/PhysRevB.10.4902	journal	December 1974
X-ray photoemission spectroscopy study of hexavalent uranium compounds Veal, B. W.; Lam, D. J.; Carnall, W. T. Physical Review B, Vol. 12, Issue 12 https://doi.org/10.1103/PhysRevB.12.5651	journal	December 1975
X-ray photoelectron-spectroscopy study of oxides of the transuranium elements Np, Pu, Am, Cm, Bk, and Cf Veal, B. W.; Lam, D. J.; Diamond, H. Physical Review B, Vol. 15, Issue 6 https://doi.org/10.1103/PhysRevB.15.2929	journal	March 1977
High-energy spectroscopic study of the occupied and unoccupied 5 f and valence states in Th and U metals Baer, Yves; Lang, Jürg Kurt Physical Review B, Vol. 21, Issue 6 https://doi.org/10.1103/PhysRevB.21.2060	journal	March 1980
Near-edge x-ray-absorption fine structure in uranium compounds Kalkowski, G.; Kaindl, G.; Brewer, W. D. Physical Review B, Vol. 35, Issue 6 https://doi.org/10.1103/PhysRevB.35.2667	journal	February 1987
X-ray-absorption sum rules in jj -coupled operators and ground-state moments of actinide ions van der Laan, Gerrit; Thole, B. T. Physical Review B, Vol. 53, Issue 21 https://doi.org/10.1103/PhysRevB.53.14458	journal	June 1996
Approximative treatment of 5 f -systems with partial localization due to intra-atomic correlations Runge, E.; Fulde, P.; Efremov, D. V. Physical Review B, Vol. 69, Issue 15 https://doi.org/10.1103/PhysRevB.69.155110	journal	April 2004
Competition between delocalization and spin-orbit splitting in the actinide 5 f states Tobin, J. G.; Moore, K. T.; Chung, B. W. Physical Review B, Vol. 72, Issue 8 https://doi.org/10.1103/PhysRevB.72.085109	journal	August 2005
Spectral functions for strongly correlated 5 f electrons Pollmann, F.; Zwicknagl, G. Physical Review B, Vol. 73, Issue 3 https://doi.org/10.1103/PhysRevB.73.035121	journal	January 2006
Angle-resolved photoemission and first-principles electronic structure of single-crystalline α -U(001) Opeil, C. P.; Schulze, R. K.; Volz, H. M. Physical Review B, Vol. 75, Issue 4 https://doi.org/10.1103/PhysRevB.75.045120	journal	January 2007
Observation of strong resonant behavior in the inverse photoelectron spectroscopy of Ce oxide Tobin, J. G.; Yu, S. W.; Chung, B. W. Physical Review B, Vol. 83, Issue 8 https://doi.org/10.1103/PhysRevB.83.085104	journal	February 2011
Oxidation and crystal field effects in uranium Tobin, J. G.; Yu, S. -W.; Booth, C. H. Physical Review B, Vol. 92, Issue 3 https://doi.org/10.1103/PhysRevB.92.035111	journal	July 2015
Covalency in oxidized uranium Tobin, J. G.; Yu, S. -W.; Qiao, R. Physical Review B, Vol. 92, Issue 4 https://doi.org/10.1103/PhysRevB.92.045130	journal	July 2015
Probing 5 f -state configurations in URu 2 Si 2 with U L III -edge resonant x-ray emission spectroscopy Booth, C. H.; Medling, S. A.; Tobin, J. G. Physical Review B, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevB.94.045121	journal	July 2016
Manifestation of electron correlation effect in 5 f states of uranium compounds revealed by 4 d – 5 f resonant photoelectron spectroscopy Fujimori, Shin-ichi; Kobata, Masaharu; Takeda, Yukiharu Physical Review B, Vol. 99, Issue 3 https://doi.org/10.1103/PhysRevB.99.035109	journal	January 2019
Orbital Specificity in the Unoccupied States of UO 2 from Resonant Inverse Photoelectron Spectroscopy Tobin, J. G.; Yu, S. -W. Physical Review Letters, Vol. 107, Issue 16 https://doi.org/10.1103/PhysRevLett.107.167406	journal	October 2011
Chemical State of Complex Uranium Oxides Kvashnina, K. O.; Butorin, S. M.; Martin, P. Physical Review Letters, Vol. 111, Issue 25 https://doi.org/10.1103/PhysRevLett.111.253002	journal	December 2013
Calculated Bulk Properties of the Actinide Metals Skriver, H. L.; Andersen, O. K.; Johansson, B. Physical Review Letters, Vol. 41, Issue 1 https://doi.org/10.1103/PhysRevLett.41.42	journal	July 1978
Failure of Russell-Saunders Coupling in the 5 f States of Plutonium Moore, K. T.; Wall, M. A.; Schwartz, A. J. Physical Review Letters, Vol. 90, Issue 19 https://doi.org/10.1103/PhysRevLett.90.196404	journal	May 2003
Applicability of the Spin-Orbit Sum Rule for the Actinide 5 f States van der Laan, G.; Moore, K. T.; Tobin, J. G. Physical Review Letters, Vol. 93, Issue 9 https://doi.org/10.1103/PhysRevLett.93.097401	journal	August 2004
5f states with spin-orbit and crystal field splittings Tobin, J. G. Journal of Vacuum Science & Technology A, Vol. 37, Issue 3 https://doi.org/10.1116/1.5087829	journal	May 2019
Electronic Structure of Heavy Fermion Uranium Compounds Studied by Core-Level Photoelectron Spectroscopy Fujimori, Shin-ichi; Ohkochi, Takuo; Kawasaki, Ikuto Journal of the Physical Society of Japan, Vol. 81, Issue 1 https://doi.org/10.1143/JPSJ.81.014703	journal	January 2012

Similar Records

The Limitations of 5f Delocalization and Dispersion

Journal Article · Sat Apr 24 20:00:00 EDT 2021 · Applied Sciences · OSTI ID:1780521

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
electronic structure
uranium

Towards the Quantification of 5f Delocalization

Citation Formats

References (39)

Similar Records

Related Subjects