On the valence fluctuation in the early actinide metals
Abstract
© 2015 Elsevier B.V. All rights reserved. Recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f 3 and f 4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δ phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f 6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.
- Authors:
-
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1248266
- Alternate Identifier(s):
- OSTI ID: 1252027; OSTI ID: 1409777; OSTI ID: 1436591
- Report Number(s):
- LLNL-JRNL-672996; LA-UR-17-24461
Journal ID: ISSN 0368-2048
- Grant/Contract Number:
- AC52-07NA27344; AC52-06NA25396; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Electron Spectroscopy and Related Phenomena
- Additional Journal Information:
- Journal Volume: 207; Journal Issue: C; Journal ID: ISSN 0368-2048
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; valence fluctuations; actinides; X-ray emission spectroscopy; density functional theory
Citation Formats
Soderlind, P., Landa, A., Tobin, J. G., Allen, P., Medling, S., Booth, C. H., Bauer, E. D., Cooley, J. C., Sokaras, D., Weng, T. -C., and Nordlund, D. On the valence fluctuation in the early actinide metals. United States: N. p., 2015.
Web. doi:10.1016/j.elspec.2015.11.014.
Soderlind, P., Landa, A., Tobin, J. G., Allen, P., Medling, S., Booth, C. H., Bauer, E. D., Cooley, J. C., Sokaras, D., Weng, T. -C., & Nordlund, D. On the valence fluctuation in the early actinide metals. United States. https://doi.org/10.1016/j.elspec.2015.11.014
Soderlind, P., Landa, A., Tobin, J. G., Allen, P., Medling, S., Booth, C. H., Bauer, E. D., Cooley, J. C., Sokaras, D., Weng, T. -C., and Nordlund, D. Tue .
"On the valence fluctuation in the early actinide metals". United States. https://doi.org/10.1016/j.elspec.2015.11.014. https://www.osti.gov/servlets/purl/1248266.
@article{osti_1248266,
title = {On the valence fluctuation in the early actinide metals},
author = {Soderlind, P. and Landa, A. and Tobin, J. G. and Allen, P. and Medling, S. and Booth, C. H. and Bauer, E. D. and Cooley, J. C. and Sokaras, D. and Weng, T. -C. and Nordlund, D.},
abstractNote = {© 2015 Elsevier B.V. All rights reserved. Recent X-ray measurements suggest a degree of valence fluctuation in plutonium and uranium intermetallics. We are applying a novel scheme, in conjunction with density functional theory, to predict 5f configuration fractions of states with valence fluctuations for the early actinide metals. For this purpose we perform constrained integer f-occupation calculations for the α phases of uranium, neptunium, and plutonium metals. For plutonium we also investigate the δ phase. The model predicts uranium and neptunium to be dominated by the f 3 and f 4 configurations, respectively, with only minor contributions from other configurations. For plutonium (both α and δ phase) the scenario is dramatically different. Here, the calculations predict a relatively even distribution between three valence configurations. The δ phase has a greater configuration fraction of f 6 compared to that of the α phase. The theory is consistent with the interpretations of modern X-ray experiments and we present resonant X-ray emission spectroscopy results for α-uranium.},
doi = {10.1016/j.elspec.2015.11.014},
journal = {Journal of Electron Spectroscopy and Related Phenomena},
number = C,
volume = 207,
place = {United States},
year = {Tue Dec 15 00:00:00 EST 2015},
month = {Tue Dec 15 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
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
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics
journal, June 2012
- Booth, C. H.; Jiang, Y.; Wang, D. L.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 26
Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy
journal, June 2014
- Booth, C. H.; Medling, S. A.; Jiang, Yu
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
First-principles phase stability, bonding, and electronic structure of actinide metals
journal, June 2014
- Söderlind, Per
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 194
Pressure-induced changes in the electronic structure of americium metal
journal, August 2011
- Söderlind, Per; Moore, K. T.; Landa, A.
- Physical Review B, Vol. 84, Issue 7
Bulk modulus and P- V relationship up to 52 GPa of neptunium metal at room temperature
journal, January 1987
- Dabos, S.; Dufour, C.; Benedict, U.
- Journal of Magnetism and Magnetic Materials, Vol. 63-64
Pressure-induced phase transition in α-Pu
journal, January 1993
- Dabos-Seignon, S.; Dancausse, J. P.; Gering, E.
- Journal of Alloys and Compounds, Vol. 190, Issue 2
X-ray diffraction study of pure plutonium under pressure
journal, March 2009
- Faure, Ph.; Genestier, C.
- Journal of Nuclear Materials, Vol. 385, Issue 1
X-ray diffraction study of δ-stabilized plutonium alloys under pressure
journal, February 2010
- Faure, Ph; Genestier, C.
- Journal of Nuclear Materials, Vol. 397, Issue 1-3
Equations of state and phase transformation of depleted uranium DU-238 by high pressure-temperature diffraction studies
journal, May 2007
- Zhao, Yusheng; Zhang, Jianzhong; Brown, Donald W.
- Physical Review B, Vol. 75, Issue 17
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource
journal, May 2013
- Sokaras, D.; Weng, T. -C.; Nordlund, D.
- Review of Scientific Instruments, Vol. 84, 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
Fluctuation effects in mixed-valence systems at zero temperature
journal, February 1982
- Kohn, W.; Lee, T. K.
- Philosophical Magazine A, Vol. 45, Issue 2
Recent spectroscopic studies of UO2
journal, January 1987
- Schoenes, Joachim
- Journal of the Chemical Society, Faraday Transactions 2, Vol. 83, Issue 7
Total and partial atomic-level widths
journal, August 1974
- Keski-Rahkonen, Olavi; Krause, Manfred O.
- Atomic Data and Nuclear Data Tables, Vol. 14, Issue 2
Computational modeling of actinide materials and complexes
journal, November 2010
- Söderlind, Per; Kotliar, G.; Haule, K.
- MRS Bulletin, Vol. 35, Issue 11
Many-Body Electronic Structure of Americium Metal
journal, January 2006
- Savrasov, Sergej Y.; Haule, Kristjan; Kotliar, Gabriel
- Physical Review Letters, Vol. 96, Issue 3
Works referencing / citing this record:
Density-functional theory for plutonium
journal, January 2019
- Söderlind, Per; Landa, A.; Sadigh, B.
- Advances in Physics, Vol. 68, Issue 1