Phase stabilization by electronic entropy in plutonium
Abstract
Abstract Plutonium metal undergoes an anomalously large 25% collapse in volume from its largest volume δ phase ( δ -Pu) to its low temperature α phase, yet the underlying thermodynamic mechanism has largely remained a mystery. Here we use magnetostriction measurements to isolate a previously hidden yet substantial electronic contribution to the entropy of δ -Pu, which we show to be crucial for the stabilization of this phase. The entropy originates from two competing instabilities of the 5 f -electron shell, which we show to drive the volume of Pu in opposing directions, depending on the temperature and volume. Using calorimetry measurements, we establish a robust thermodynamic connection between the two excitation energies, the atomic volume, and the previously reported excess entropy of δ -Pu at elevated temperatures.
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1619833
- Alternate Identifier(s):
- OSTI ID: 1825427
- Report Number(s):
- LA-UR-19-20229
Journal ID: ISSN 2041-1723; 3159; PII: 11166
- Grant/Contract Number:
- 89233218CNA000001; 20180025DR
- Resource Type:
- Published Article
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Name: Nature Communications Journal Volume: 10 Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
Citation Formats
Harrison, N., Betts, J. B., Wartenbe, M. R., Balakirev, F. F., Richmond, S., Jaime, M., and Tobash, P. H. Phase stabilization by electronic entropy in plutonium. United Kingdom: N. p., 2019.
Web. doi:10.1038/s41467-019-11166-0.
Harrison, N., Betts, J. B., Wartenbe, M. R., Balakirev, F. F., Richmond, S., Jaime, M., & Tobash, P. H. Phase stabilization by electronic entropy in plutonium. United Kingdom. https://doi.org/10.1038/s41467-019-11166-0
Harrison, N., Betts, J. B., Wartenbe, M. R., Balakirev, F. F., Richmond, S., Jaime, M., and Tobash, P. H. Thu .
"Phase stabilization by electronic entropy in plutonium". United Kingdom. https://doi.org/10.1038/s41467-019-11166-0.
@article{osti_1619833,
title = {Phase stabilization by electronic entropy in plutonium},
author = {Harrison, N. and Betts, J. B. and Wartenbe, M. R. and Balakirev, F. F. and Richmond, S. and Jaime, M. and Tobash, P. H.},
abstractNote = {Abstract Plutonium metal undergoes an anomalously large 25% collapse in volume from its largest volume δ phase ( δ -Pu) to its low temperature α phase, yet the underlying thermodynamic mechanism has largely remained a mystery. Here we use magnetostriction measurements to isolate a previously hidden yet substantial electronic contribution to the entropy of δ -Pu, which we show to be crucial for the stabilization of this phase. The entropy originates from two competing instabilities of the 5 f -electron shell, which we show to drive the volume of Pu in opposing directions, depending on the temperature and volume. Using calorimetry measurements, we establish a robust thermodynamic connection between the two excitation energies, the atomic volume, and the previously reported excess entropy of δ -Pu at elevated temperatures.},
doi = {10.1038/s41467-019-11166-0},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {7}
}
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Works referenced in this record:
Magnetic-field, pressure, and temperature scaling of the first-order valence transition in pure and doped YbInCu 4
journal, July 1997
- Immer, C. D.; Sarrao, J. L.; Fisk, Z.
- Physical Review B, Vol. 56, Issue 1
Equilibrium properties of delta-Pu: LDA+ U calculations (LDAequiv local density approximation)
journal, February 2000
- Bouchet, J.; Siberchicot, B.; Jollet, F.
- Journal of Physics: Condensed Matter, Vol. 12, Issue 8
Valence fluctuation phenomena
journal, January 1981
- Lawrence, J. M.; Riseborough, P. S.; Parks, R. D.
- Reports on Progress in Physics, Vol. 44, Issue 1
Electronic and phonon properties of six crystalline phases of Pu metal
journal, December 1998
- Wallace, Duane C.
- Physical Review B, Vol. 58, Issue 23
Fiber Bragg Grating Dilatometry in Extreme Magnetic Field and Cryogenic Conditions
journal, November 2017
- Jaime, Marcelo; Corvalán Moya, Carolina; Weickert, Franziska
- Sensors, Vol. 17, Issue 11
Melting of the light actinides
journal, January 2000
- Lawson, A. C.; Artinez, B. M.; Roberts, J. A.
- Philosophical Magazine B, Vol. 80, Issue 1
Self-interaction-corrected local spin density theory of electron localization in actinides
journal, September 2007
- Svane, A.; Petit, L.; Szotek, Z.
- Physical Review B, Vol. 76, Issue 11
Electronic properties of f -electron metals using the generalized gradient approximation
journal, September 1994
- Söderlind, P.; Eriksson, O.; Johansson, B.
- Physical Review B, Vol. 50, Issue 11
Suppression of the γ–α structural phase transition in Ce 0.8 La 0.1 Th 0.1 by large magnetic fields
journal, February 2005
- Drymiotis, F.; Singleton, J.; Harrison, N.
- Journal of Physics: Condensed Matter, Vol. 17, Issue 7
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997
- Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
- Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
Piezomagnetism and magnetoelastic memory in uranium dioxide
journal, July 2017
- Jaime, M.; Saul, A.; Salamon, M.
- Nature Communications, Vol. 8, Issue 1
Volume magnetostriction of intermediate valence systems
journal, February 1985
- Häfner, H. U.
- Journal of Magnetism and Magnetic Materials, Vol. 47-48
Volume magnetostriction of rare-earth metals with unstable 4f shells
journal, January 1986
- Zieglowski, J.; Hafner, H. U.; Wohlleben, D.
- Physical Review Letters, Vol. 56, Issue 2
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
Magnetic and magnetoelastic properties of single crystal
journal, February 1988
- Barthem, V. M. T. S.; Gignoux, D.; Naït-Saada, A.
- Physical Review B, Vol. 37, Issue 4
Dual nature of electrons: Effect of intra-atomic correlations on hopping anisotropies
journal, March 2004
- Efremov, D. V.; Hasselmann, N.; Runge, E.
- Physical Review B, Vol. 69, Issue 11
Magnetostriction in metals
journal, November 1971
- Chandrasekhar, B. S.; Fawcett, E.
- Advances in Physics, Vol. 20, Issue 88
Correlated electrons in δ-plutonium within a dynamical mean-field picture
journal, April 2001
- Savrasov, S. Y.; Kotliar, G.; Abrahams, E.
- Nature, Vol. 410, Issue 6830
Spin-polarized relativistic linear-muffin-tin-orbital method: Volume-dependent electronic structure and magnetic moment of plutonium
journal, June 1991
- Solovyev, I. V.; Liechtenstein, A. I.; Gubanov, V. A.
- Physical Review B, Vol. 43, Issue 18
Cancellation of spin and orbital magnetic moments in δ-Pu: Theory
journal, October 2007
- Söderlind, Per
- Journal of Alloys and Compounds, Vol. 444-445
Density-functional investigation of magnetism in -Pu
journal, November 2002
- Söderlind, Per; Landa, Alex; Sadigh, Babak
- Physical Review B, Vol. 66, Issue 20
A unified and efficient theory for the structural properties of actinides and phases of plutonium
journal, September 2018
- Amadon, Bernard; Dorado, Boris
- Journal of Physics: Condensed Matter, Vol. 30, Issue 40
Phase stability and phase transformations in Pu–Ga alloys
journal, January 2004
- Hecker, S. S.; Harbur, D. R.; Zocco, T. G.
- Progress in Materials Science, Vol. 49, Issue 3-4
Gallium stabilization of : Density-functional calculations
journal, November 2005
- Sadigh, Babak; Wolfer, Wilhelm G.
- Physical Review B, Vol. 72, Issue 20
Heat capacity measurements on a thin ribbon sample of Zr0.55Al0.10Ni0.05Cu0.30 glassy alloy and Apiezon N high vacuum grease using a Quantum Design Physical Property Measurement System
journal, May 2009
- Moriya, Yosuke; Kawaji, Hitoshi; Atake, Tooru
- Cryogenics, Vol. 49, Issue 5
Density-Functional Calculations of , , , , , and Plutonium
journal, May 2004
- Söderlind, Per; Sadigh, Babak
- Physical Review Letters, Vol. 92, Issue 18
Phonon density of states of - and -plutonium by inelastic x-ray scattering
journal, February 2009
- Manley, M. E.; Said, A. H.; Fluss, M. J.
- Physical Review B, Vol. 79, Issue 5
Hidden disorder in the transformation of Pu-1.9 at. Ga
journal, June 2012
- Jeffries, J. R.; Manley, M. E.; Wall, M. A.
- Physical Review B, Vol. 85, Issue 22
Influence of point defects and impurities on the dynamical stability of δ -plutonium
journal, May 2017
- Dorado, B.; Bieder, J.; Torrent, M.
- Journal of Physics: Condensed Matter, Vol. 29, Issue 24
Absence of magnetic moments in plutonium
journal, August 2005
- Lashley, J. C.; Lawson, A.; McQueeney, R. J.
- Physical Review B, Vol. 72, Issue 5
Magnetism or bonding: A nearly periodic table of transition elements
journal, March 1983
- Smith, J. L.; Kmetko, E. A.
- Journal of the Less Common Metals, Vol. 90, Issue 1
Simple Scaling Approach to the Volume Magnetostriction in Unstable-Moment Systems
journal, April 1986
- Thalmeier, P.; Fulde, P.
- Europhysics Letters (EPL), Vol. 1, Issue 7
Fluctuating valence in a correlated solid and the anomalous properties of δ-plutonium
journal, March 2007
- Shim, J. H.; Haule, K.; Kotliar, G.
- Nature, Vol. 446, Issue 7135
First-order valence transition in YbInCu 4 in the ( B , T )-plane
journal, November 2000
- Dzero, M. O.; Gor'kov, L. P.; Zvezdin, A. K.
- Journal of Physics: Condensed Matter, Vol. 12, Issue 47
Coulomb- U and magnetic-moment collapse in δ-Pu
journal, February 2005
- Shick, A. B.; Drchal, V.; Havela, L.
- Europhysics Letters (EPL), Vol. 69, Issue 4
Phase stability and phase transformations in plutonium and plutonium-gallium alloys
journal, August 2004
- Mitchell, Jeremy N.; Schwartz, Daniel S.; Stan, Marius
- Metallurgical and Materials Transactions A, Vol. 35, Issue 8
Phonon Dispersions of fcc -Plutonium-Gallium by Inelastic X-ray Scattering
journal, August 2003
- Wong, J.
- Science, Vol. 301, Issue 5636
Giant magnetic Grüneisen parameters in nearly ferromagnetic and heavy-fermion systems
journal, April 1988
- Kaiser, A. B.; Fulde, P.
- Physical Review B, Vol. 37, Issue 10
Spectral properties of -plutonium: Sensitivity to occupancy
journal, December 2007
- Zhu, Jian-Xin; McMahan, A. K.; Jones, M. D.
- Physical Review B, Vol. 76, Issue 24
The valence-fluctuating ground state of plutonium
journal, July 2015
- Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan
- Science Advances, Vol. 1, Issue 6
The dual nature of 5f electrons and the origin of heavy fermions in U compounds
journal, July 2003
- Zwicknagl, G.; Fulde, P.
- Journal of Physics: Condensed Matter, Vol. 15, Issue 28
The mixed valence energy parameters of some Ce and Yb systems
journal, February 1985
- Wittershagen, B.; Wohlleben, D.
- Journal of Magnetism and Magnetic Materials, Vol. 47-48
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
Experimental Electronic Heat Capacities of - and -Plutonium: Heavy-Fermion Physics in an Element
journal, November 2003
- Lashley, J. C.; Singleton, J.; Migliori, A.
- Physical Review Letters, Vol. 91, Issue 20
A novel electronic configuration of the 5f states in δ-plutonium as revealed by the photo-electron spectra
journal, April 2004
- Wills, J. M.; Eriksson, O.; Delin, A.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 135, Issue 2-3
Calculated Phonon Spectra of Plutonium at High Temperatures
journal, May 2003
- Dai, X.
- Science, Vol. 300, Issue 5621
Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions
journal, January 1996
- Georges, Antoine; Kotliar, Gabriel; Krauth, Werner
- Reviews of Modern Physics, Vol. 68, Issue 1
The Transition of Cerium Is Entropy Driven
journal, February 2006
- Amadon, B.; Biermann, S.; Georges, A.
- Physical Review Letters, Vol. 96, Issue 6
Origin of the multiple configurations that drive the response of δ-plutonium’s elastic moduli to temperature
journal, September 2016
- Migliori, Albert; Söderlind, Per; Landa, Alexander
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 40
Novel electronic configuration in ∂−Pu
journal, June 1999
- Eriksson, Olle; Becker, J. D.; Balatsky, A. V.
- Journal of Alloys and Compounds, Vol. 287, Issue 1-2
Invar model for δ-phase Pu: thermal expansion, elastic and magnetic properties
journal, June 2006
- Lawson, A. C.; Roberts, J. A.; Martinez, B.
- Philosophical Magazine, Vol. 86, Issue 17-18