Phase stabilization by electronic entropy in plutonium

Harrison, Neil; Betts, Jonathan Bobby; Balakirev, Fedor Fedorovich; Richmond, Scott; Jaime, Marcelo; Tobash, Paul H.

doi:10.1038/s41467-019-11166-0

Title: Phase stabilization by electronic entropy in plutonium

Journal Article · 18 July 2019 · Nature Communications

DOI: https://doi.org/10.1038/s41467-019-11166-0 · OSTI ID:1619833

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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 5f-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.

View Journal Article

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001; 20180025DR

OSTI ID:: 1619833

Alternate ID(s):: OSTI ID: 1825427

Report Number(s):: LA-UR-19-20229; TRN: US2215805

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

References (77)

Magnetic-field, pressure, and temperature scaling of the first-order valence transition in pure and doped YbInCu 4 Immer, C. D.; Sarrao, J. L.; Fisk, Z. Physical Review B, Vol. 56, Issue 1 https://doi.org/10.1103/PhysRevB.56.71	journal	July 1997
Equilibrium properties of delta-Pu: LDA+ U calculations (LDAequiv local density approximation) Bouchet, J.; Siberchicot, B.; Jollet, F. Journal of Physics: Condensed Matter, Vol. 12, Issue 8 https://doi.org/10.1088/0953-8984/12/8/315	journal	February 2000
Valence fluctuation phenomena Lawrence, J. M.; Riseborough, P. S.; Parks, R. D. Reports on Progress in Physics, Vol. 44, Issue 1 https://doi.org/10.1088/0034-4885/44/1/001	journal	January 1981
Electronic and phonon properties of six crystalline phases of Pu metal Wallace, Duane C. Physical Review B, Vol. 58, Issue 23 https://doi.org/10.1103/PhysRevB.58.15433	journal	December 1998
Fiber Bragg Grating Dilatometry in Extreme Magnetic Field and Cryogenic Conditions Jaime, Marcelo; Corvalán Moya, Carolina; Weickert, Franziska Sensors, Vol. 17, Issue 11 https://doi.org/10.3390/s17112572	journal	November 2017
Melting of the light actinides Lawson, A. C.; Artinez, B. M.; Roberts, J. A. Philosophical Magazine B, Vol. 80, Issue 1 https://doi.org/10.1080/13642810008218339	journal	January 2000
Self-interaction-corrected local spin density theory of 5 f electron localization in actinides Svane, A.; Petit, L.; Szotek, Z. Physical Review B, Vol. 76, Issue 11 https://doi.org/10.1103/PhysRevB.76.115116	journal	September 2007
Electronic properties of f -electron metals using the generalized gradient approximation Söderlind, P.; Eriksson, O.; Johansson, B. Physical Review B, Vol. 50, Issue 11 https://doi.org/10.1103/PhysRevB.50.7291	journal	September 1994
Suppression of the γ–α structural phase transition in Ce _0.8 La _0.1 Th _0.1 by large magnetic fields Drymiotis, F.; Singleton, J.; Harrison, N. Journal of Physics: Condensed Matter, Vol. 17, Issue 7 https://doi.org/10.1088/0953-8984/17/7/L01	journal	February 2005
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I. Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808 https://doi.org/10.1088/0953-8984/9/4/002	journal	January 1997
Piezomagnetism and magnetoelastic memory in uranium dioxide Jaime, M.; Saul, A.; Salamon, M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00096-4	journal	July 2017
Volume magnetostriction of intermediate valence systems Häfner, H. U. Journal of Magnetism and Magnetic Materials, Vol. 47-48 https://doi.org/10.1016/0304-8853(85)90422-6	journal	February 1985
Volume magnetostriction of rare-earth metals with unstable 4f shells Zieglowski, J.; Hafner, H. U.; Wohlleben, D. Physical Review Letters, Vol. 56, Issue 2 https://doi.org/10.1103/PhysRevLett.56.193	journal	January 1986
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
Magnetic and magnetoelastic properties of PrNi 5 single crystal Barthem, V. M. T. S.; Gignoux, D.; Naït-Saada, A. Physical Review B, Vol. 37, Issue 4 https://doi.org/10.1103/PhysRevB.37.1733	journal	February 1988
Dual nature of 5 f electrons: Effect of intra-atomic correlations on hopping anisotropies Efremov, D. V.; Hasselmann, N.; Runge, E. Physical Review B, Vol. 69, Issue 11 https://doi.org/10.1103/PhysRevB.69.115114	journal	March 2004
Magnetostriction in metals Chandrasekhar, B. S.; Fawcett, E. Advances in Physics, Vol. 20, Issue 88 https://doi.org/10.1080/00018737100101351	journal	November 1971
Correlated electrons in δ-plutonium within a dynamical mean-field picture Savrasov, S. Y.; Kotliar, G.; Abrahams, E. Nature, Vol. 410, Issue 6830 https://doi.org/10.1038/35071035	journal	April 2001
Cancellation of spin and orbital magnetic moments in δ-Pu: Theory Söderlind, Per Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.084	journal	October 2007
Density-functional investigation of magnetism in δ -Pu Söderlind, Per; Landa, Alex; Sadigh, Babak Physical Review B, Vol. 66, Issue 20 https://doi.org/10.1103/PhysRevB.66.205109	journal	November 2002
A unified and efficient theory for the structural properties of actinides and phases of plutonium Amadon, Bernard; Dorado, Boris Journal of Physics: Condensed Matter, Vol. 30, Issue 40 https://doi.org/10.1088/1361-648X/aadc7a	journal	September 2018
Phase stability and phase transformations in Pu–Ga alloys Hecker, S. S.; Harbur, D. R.; Zocco, T. G. Progress in Materials Science, Vol. 49, Issue 3-4 https://doi.org/10.1016/S0079-6425(03)00032-X	journal	January 2004
Gallium stabilization of δ − Pu : Density-functional calculations Sadigh, Babak; Wolfer, Wilhelm G. Physical Review B, Vol. 72, Issue 20 https://doi.org/10.1103/PhysRevB.72.205122	journal	November 2005
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 Moriya, Yosuke; Kawaji, Hitoshi; Atake, Tooru Cryogenics, Vol. 49, Issue 5 https://doi.org/10.1016/j.cryogenics.2009.01.001	journal	May 2009
Density-Functional Calculations of α , β , γ , δ , δ ′ , and ϵ Plutonium Söderlind, Per; Sadigh, Babak Physical Review Letters, Vol. 92, Issue 18 https://doi.org/10.1103/PhysRevLett.92.185702	journal	May 2004
Phonon density of states of α - and δ -plutonium by inelastic x-ray scattering Manley, M. E.; Said, A. H.; Fluss, M. J. Physical Review B, Vol. 79, Issue 5 https://doi.org/10.1103/PhysRevB.79.052301	journal	February 2009
Hidden disorder in the α ′ → δ transformation of Pu-1.9 at. % Ga Jeffries, J. R.; Manley, M. E.; Wall, M. A. Physical Review B, Vol. 85, Issue 22 https://doi.org/10.1103/PhysRevB.85.224104	journal	June 2012
Absence of magnetic moments in plutonium Lashley, J. C.; Lawson, A.; McQueeney, R. J. Physical Review B, Vol. 72, Issue 5 https://doi.org/10.1103/PhysRevB.72.054416	journal	August 2005
Magnetism or bonding: A nearly periodic table of transition elements Smith, J. L.; Kmetko, E. A. Journal of the Less Common Metals, Vol. 90, Issue 1 https://doi.org/10.1016/0022-5088(83)90119-4	journal	March 1983
Simple Scaling Approach to the Volume Magnetostriction in Unstable-Moment Systems Thalmeier, P.; Fulde, P. Europhysics Letters (EPL), Vol. 1, Issue 7 https://doi.org/10.1209/0295-5075/1/7/006	journal	April 1986
Fluctuating valence in a correlated solid and the anomalous properties of δ-plutonium Shim, J. H.; Haule, K.; Kotliar, G. Nature, Vol. 446, Issue 7135 https://doi.org/10.1038/nature05647	journal	March 2007
First-order valence transition in YbInCu 4 in the ( B , T )-plane Dzero, M. O.; Gor'kov, L. P.; Zvezdin, A. K. Journal of Physics: Condensed Matter, Vol. 12, Issue 47 https://doi.org/10.1088/0953-8984/12/47/102	journal	November 2000
Coulomb- U and magnetic-moment collapse in δ-Pu Shick, A. B.; Drchal, V.; Havela, L. Europhysics Letters (EPL), Vol. 69, Issue 4 https://doi.org/10.1209/epl/i2004-10380-5	journal	February 2005
Phase stability and phase transformations in plutonium and plutonium-gallium alloys Mitchell, Jeremy N.; Schwartz, Daniel S.; Stan, Marius Metallurgical and Materials Transactions A, Vol. 35, Issue 8 https://doi.org/10.1007/s11661-006-0206-8	journal	August 2004
Phase Stability and Phase Transformations in Pu—Ga Alloys Hecker, S. S.; Harbur, D. R.; Zocco, T. G. ChemInform, Vol. 35, Issue 42 https://doi.org/10.1002/chin.200442250	journal	October 2004
Phonon Dispersions of fcc -Plutonium-Gallium by Inelastic X-ray Scattering Wong, J. Science, Vol. 301, Issue 5636 https://doi.org/10.1126/science.1087179	journal	August 2003
Spectral properties of δ -plutonium: Sensitivity to 5 f occupancy Zhu, Jian-Xin; McMahan, A. K.; Jones, M. D. Physical Review B, Vol. 76, Issue 24 https://doi.org/10.1103/PhysRevB.76.245118	journal	December 2007
The valence-fluctuating ground state of plutonium Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan Science Advances, Vol. 1, Issue 6 https://doi.org/10.1126/sciadv.1500188	journal	July 2015
Experimental electronic heat capacities of $α-$ and $δ-$Plutonium; heavy-fermion physics in an element Lashley, J. C.; Singleton, J.; Migliori, A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0306257	text	January 2003
The dual nature of 5f electrons and the origin of heavy fermions in U compounds Zwicknagl, G.; Fulde, P. Journal of Physics: Condensed Matter, Vol. 15, Issue 28 https://doi.org/10.1088/0953-8984/15/28/302	journal	July 2003
The mixed valence energy parameters of some Ce and Yb systems Wittershagen, B.; Wohlleben, D. Journal of Magnetism and Magnetic Materials, Vol. 47-48 https://doi.org/10.1016/0304-8853(85)90363-4	journal	February 1985
Nature of the 5 f states in actinide metals Moore, Kevin T.; van der Laan, Gerrit Reviews of Modern Physics, Vol. 81, Issue 1 https://doi.org/10.1103/RevModPhys.81.235	journal	February 2009
Experimental Electronic Heat Capacities of α - and δ -Plutonium: Heavy-Fermion Physics in an Element Lashley, J. C.; Singleton, J.; Migliori, A. Physical Review Letters, Vol. 91, Issue 20 https://doi.org/10.1103/PhysRevLett.91.205901	journal	November 2003
A novel electronic configuration of the 5f states in δ-plutonium as revealed by the photo-electron spectra Wills, J. M.; Eriksson, O.; Delin, A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 135, Issue 2-3 https://doi.org/10.1016/j.elspec.2004.02.169	journal	April 2004
The dual nature of 5f electrons and origin of heavy fermions in U compounds Zwicknagl, G.; Fulde, P. arXiv https://doi.org/10.48550/arxiv.cond-mat/0211706	text	January 2002
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics Booth, C. H.; Jiang, Yu; Wang, D. L. arXiv https://doi.org/10.48550/arxiv.1208.2234	text	January 2012
Calculated Phonon Spectra of Plutonium at High Temperatures Dai, X. Science, Vol. 300, Issue 5621 https://doi.org/10.1126/science.1083428	journal	May 2003
Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions Georges, Antoine; Kotliar, Gabriel; Krauth, Werner Reviews of Modern Physics, Vol. 68, Issue 1 https://doi.org/10.1103/RevModPhys.68.13	journal	January 1996
The α − γ Transition of Cerium Is Entropy Driven Amadon, B.; Biermann, S.; Georges, A. Physical Review Letters, Vol. 96, Issue 6 https://doi.org/10.1103/PhysRevLett.96.066402	journal	February 2006
Origin of the multiple configurations that drive the response of δ-plutonium’s elastic moduli to temperature Migliori, Albert; Söderlind, Per; Landa, Alexander Proceedings of the National Academy of Sciences, Vol. 113, Issue 40 https://doi.org/10.1073/pnas.1609215113	journal	September 2016
Novel electronic configuration in ∂−Pu Eriksson, Olle; Becker, J. D.; Balatsky, A. V. Journal of Alloys and Compounds, Vol. 287, Issue 1-2 https://doi.org/10.1016/S0925-8388(99)00063-8	journal	June 1999
Invar model for δ-phase Pu: thermal expansion, elastic and magnetic properties Lawson, A. C.; Roberts, J. A.; Martinez, B. Philosophical Magazine, Vol. 86, Issue 17-18 https://doi.org/10.1080/14786430500155262	journal	June 2006
Theory of magnetic impurities in metals Hirst, L. L. Physik der Kondensierten Materie, Vol. 11, Issue 3 https://doi.org/10.1007/bf02422643	journal	August 1970
Phase stability and phase transformations in plutonium and plutonium-gallium alloys Mitchell, Jeremy N.; Schwartz, Daniel S.; Stan, Marius Metallurgical and Materials Transactions A, Vol. 35, Issue 8 https://doi.org/10.1007/s11661-006-0206-8	journal	August 2004
Magnetism or bonding: A nearly periodic table of transition elements Smith, J. L.; Kmetko, E. A. Journal of the Less Common Metals, Vol. 90, Issue 1 https://doi.org/10.1016/0022-5088(83)90119-4	journal	March 1983
The mixed valence energy parameters of some Ce and Yb systems Wittershagen, B.; Wohlleben, D. Journal of Magnetism and Magnetic Materials, Vol. 47-48 https://doi.org/10.1016/0304-8853(85)90363-4	journal	February 1985
Volume magnetostriction of intermediate valence systems Häfner, H. U. Journal of Magnetism and Magnetic Materials, Vol. 47-48 https://doi.org/10.1016/0304-8853(85)90422-6	journal	February 1985
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 Moriya, Yosuke; Kawaji, Hitoshi; Atake, Tooru Cryogenics, Vol. 49, Issue 5 https://doi.org/10.1016/j.cryogenics.2009.01.001	journal	May 2009
Cancellation of spin and orbital magnetic moments in δ-Pu: Theory Söderlind, Per Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.084	journal	October 2007
Correlated electrons in δ-plutonium within a dynamical mean-field picture Savrasov, S. Y.; Kotliar, G.; Abrahams, E. Nature, Vol. 410, Issue 6830 https://doi.org/10.1038/35071035	journal	April 2001
Fluctuating valence in a correlated solid and the anomalous properties of δ-plutonium Shim, J. H.; Haule, K.; Kotliar, G. Nature, Vol. 446, Issue 7135 https://doi.org/10.1038/nature05647	journal	March 2007
Piezomagnetism and magnetoelastic memory in uranium dioxide Jaime, M.; Saul, A.; Salamon, M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00096-4	journal	July 2017
Origin of the multiple configurations that drive the response of δ-plutonium’s elastic moduli to temperature Migliori, Albert; Söderlind, Per; Landa, Alexander Proceedings of the National Academy of Sciences, Vol. 113, Issue 40 https://doi.org/10.1073/pnas.1609215113	journal	September 2016
Magnetostriction in metals Chandrasekhar, B. S.; Fawcett, E. Advances in Physics, Vol. 20, Issue 88 https://doi.org/10.1080/00018737100101351	journal	November 1971
Melting of the light actinides Lawson, A. C.; Artinez, B. M.; Roberts, J. A. Philosophical Magazine B, Vol. 80, Issue 1 https://doi.org/10.1080/13642810008218339	journal	January 2000
Invar model for δ-phase Pu: thermal expansion, elastic and magnetic properties Lawson, A. C.; Roberts, J. A.; Martinez, B. Philosophical Magazine, Vol. 86, Issue 17-18 https://doi.org/10.1080/14786430500155262	journal	June 2006
The dual nature of 5f electrons and the origin of heavy fermions in U compounds Zwicknagl, G.; Fulde, P. Journal of Physics: Condensed Matter, Vol. 15, Issue 28 https://doi.org/10.1088/0953-8984/15/28/302	journal	July 2003
First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I. Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808 https://doi.org/10.1088/0953-8984/9/4/002	journal	January 1997
Influence of point defects and impurities on the dynamical stability of δ -plutonium Dorado, B.; Bieder, J.; Torrent, M. Journal of Physics: Condensed Matter, Vol. 29, Issue 24 https://doi.org/10.1088/1361-648x/aa6eb7	journal	May 2017
Giant magnetic Grüneisen parameters in nearly ferromagnetic and heavy-fermion systems Kaiser, A. B.; Fulde, P. Physical Review B, Vol. 37, Issue 10 https://doi.org/10.1103/physrevb.37.5357	journal	April 1988
Spin-polarized relativistic linear-muffin-tin-orbital method: Volume-dependent electronic structure and magnetic moment of plutonium Solovyev, I. V.; Liechtenstein, A. I.; Gubanov, V. A. Physical Review B, Vol. 43, Issue 18 https://doi.org/10.1103/physrevb.43.14414	journal	June 1991
The valence-fluctuating ground state of plutonium Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan Science Advances, Vol. 1, Issue 6 https://doi.org/10.1126/sciadv.1500188	journal	July 2015
Calculated Phonon Spectra of Plutonium at High Temperatures Dai, X. Science, Vol. 300, Issue 5621 https://doi.org/10.1126/science.1083428	journal	May 2003
Coulomb- U and magnetic-moment collapse in δ-Pu Shick, A. B.; Drchal, V.; Havela, L. Europhysics Letters (EPL), Vol. 69, Issue 4 https://doi.org/10.1209/epl/i2004-10380-5	journal	February 2005
Fiber Bragg Grating Dilatometry in Extreme Magnetic Field and Cryogenic Conditions Jaime, Marcelo; Corvalán Moya, Carolina; Weickert, Franziska Sensors, Vol. 17, Issue 11 https://doi.org/10.3390/s17112572	journal	November 2017
Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics Booth, C. H.; Jiang, Yu; Wang, D. L. arXiv https://doi.org/10.48550/arxiv.1208.2234	text	January 2012
First order valence transition in YbInCu_4 in the (B,T) - plane Dzero, M. O.; Gor'kov, L. P.; Zvezdin, A. K. arXiv https://doi.org/10.48550/arxiv.cond-mat/0008134	text	January 2000

Cited By (2)

Unusual phase boundary of the magnetic-field-tuned valence transition in CeOs 4 Sb 12 Götze, K.; Pearce, M. J.; Goddard, P. A. Physical Review B, Vol. 101, Issue 7 https://doi.org/10.1103/physrevb.101.075102	journal	February 2020
Electronically driven collapse of the bulk modulus in δ -plutonium Harrison, Neil Proceedings of the National Academy of Sciences, Vol. 117, Issue 9 https://doi.org/10.1073/pnas.1918281117	journal	February 2020

Similar Records

Indications of flat bands driving the δ to α volume collapse of plutonium

Journal Article · 2024 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:2305438

Harrison, Neil; Chappell, Greta L.; Tobash, Paul H.

Indications of flat bands driving the δ to α volume collapse of plutonium

Technical Report · 2024 · OSTI ID:2377700

Harrison, Neil; Chappell, Greta Leigh; Tobash, Paul H.

Pseudogap in elemental plutonium

Journal Article · 2022 · Physical Review. B · OSTI ID:1874164

Wartenbe, Mark; Tobash, Paul H.; Singleton, John; +3 more

Related Subjects

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Title: Phase stabilization by electronic entropy in plutonium

Citation Formats

References (77)

Cited By (2)

Similar Records

Related Subjects