Assessing Relativistic Effects and Electron Correlation in the Actinide Metals Th to Pu

Sadigh, Babak; Kutepov, Andrey; Landa, Alexander; Söderlind, Per

doi:10.3390/app9235020

Title: Assessing Relativistic Effects and Electron Correlation in the Actinide Metals Th to Pu

Journal Article · Thu Nov 21 00:00:00 EST 2019 · Applied Sciences

DOI:https://doi.org/10.3390/app9235020· OSTI ID:1579488

Sadigh, Babak ^[1];

^[2]; Landa, Alexander ^[1]; Söderlind, Per ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Density functional theory (DFT) calculations are employed to explore and assess the effects of the relativistic spin–orbit interaction and electron correlations in the actinide elements. Specifically, we address electron correlations in terms of an intra-atomic Coulomb interaction with a Hubbard U parameter (DFT + U). Contrary to recent beliefs, we show that for the ground-state properties of the light actinide elements Th to Pu, the DFT + U makes its best predictions for U = 0. Actually, our modeling suggests that the most popular DFT + U formulation leads to the wrong ground-state phase for plutonium. Instead, extending DFT and the generalized gradient approximation (GGA) with orbital–orbital interaction (orbital polarization; OP) is the most accurate approach. We believe the confusion in the literature on the subject mostly originates from incorrectly accounting for the spin–orbit (SO) interaction for the p1/2 state, which is not treated in any of the widely used pseudopotential plane-wave codes. Here, we show that for the actinides it suffices to simply discard the SO coupling for the p states for excellent accuracy. We thus describe a formalism within the projector-augmented-wave (PAW) scheme that allows for spin–orbit coupling, orbital polarization, and non-collinear magnetism, while retaining an efficient calculation of Hellmann–Feynman forces. We present results of the ground-state phases of all the light actinide metals (Th to Pu). Furthermore, we conclude that the contribution from OP is generally small, but substantial in plutonium.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0012704; AC52-07NA27344

OSTI ID:: 1579488

Alternate ID(s):: OSTI ID: 1602654

Report Number(s):: BNL-212394-2019-JAAM; LLNL-JRNL-792557; ASPCC7; TRN: US2102183

Journal Information:: Applied Sciences, Vol. 9, Issue 23; ISSN 2076-3417

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 16 works

Citation information provided by
Web of Science

References (52)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Anomalous atomic volume of α-Pu Kollár, J.; Vitos, L.; Skriver, H. L. Physical Review B, Vol. 55, Issue 23 https://doi.org/10.1103/PhysRevB.55.15353	journal	June 1997
Calculated thermodynamic properties of plutonium metal Robert, G.; Pasturel, A.; Siberchicot, B. Journal of Physics: Condensed Matter, Vol. 15, Issue 49 https://doi.org/10.1088/0953-8984/15/49/015	journal	November 2003
Density-functional study of Zr-based actinide alloys: 2. U–Pu–Zr system Landa, A.; Söderlind, P.; Turchi, P. E. A. Journal of Nuclear Materials, Vol. 393, Issue 1 https://doi.org/10.1016/j.jnucmat.2009.05.014	journal	August 2009
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
High-temperature phonon stabilization of $γ$ -uranium from relativistic first-principles theory Söderlind, Per; Grabowski, B.; Yang, L. Physical Review B, Vol. 85, Issue 6 https://doi.org/10.1103/PhysRevB.85.060301	journal	February 2012
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
Phase equilibria in the U-Si system from first-principles calculations Noordhoek, Mark J.; Besmann, Theodore M.; Andersson, David Journal of Nuclear Materials, Vol. 479 https://doi.org/10.1016/j.jnucmat.2016.07.006	journal	October 2016
Electronic structure and magnetic state of transuranium metals under pressure Lukoyanov, A. V.; Shorikov, A. O.; Bystrushkin, V. B. Journal of Physics: Condensed Matter, Vol. 22, Issue 49 https://doi.org/10.1088/0953-8984/22/49/495501	journal	November 2010
Orbital polarization in narrow-band systems: Application to volume collapses in light lanthanides Eriksson, Olle; Brooks, M. S. S.; Johansson, Börje Physical Review B, Vol. 41, Issue 10 https://doi.org/10.1103/PhysRevB.41.7311	journal	April 1990
New muffin tin orbital band calculations of equilibrium properties and electronic structure of actinide metals Pénicaud, M. Journal of Alloys and Compounds, Vol. 213-214 https://doi.org/10.1016/0925-8388(94)90946-6	journal	October 1994
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Polymorph transitions in uranium at low temperatures: first-principles investigation Migdal, K. P.; Yanilkin, A. V. Modelling and Simulation in Materials Science and Engineering, Vol. 26, Issue 2 https://doi.org/10.1088/1361-651X/aa9f35	journal	January 2018
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
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
The ab initio ground state properties and magnetic structure of plutonium Kutepov, A. L.; Kutepova, S. G. Journal of Physics: Condensed Matter, Vol. 15, Issue 17 https://doi.org/10.1088/0953-8984/15/17/315	journal	April 2003
Thermal expansion of neptunium Cort, B. Journal of the Less Common Metals, Vol. 135, Issue 1 https://doi.org/10.1016/0022-5088(87)90350-X	journal	October 1987
Thermodynamic evaluation of the Np–Zr system using CALPHAD and ab initio methods Xiong, Wei; Xie, Wei; Morgan, Dane Journal of Nuclear Materials, Vol. 452, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2014.06.023	journal	September 2014
Pseudopotential for plane-wave density functional theory studies of metallic uranium Iasir, A. Rafi M.; Hammond, Karl D. Computational Materials Science, Vol. 171 https://doi.org/10.1016/j.commatsci.2019.109221	journal	January 2020
Ab initio energetics for modeling phase stability of the Np-U system Xie, Wei; Chang, Y. Austin; Morgan, Dane Journal of Nuclear Materials, Vol. 479 https://doi.org/10.1016/j.jnucmat.2016.07.011	journal	October 2016
Correlation and relativistic effects in U metal and U-Zr alloy: Validation of ab initio approaches Xie, Wei; Xiong, Wei; Marianetti, Chris A. Physical Review B, Vol. 88, Issue 23 https://doi.org/10.1103/PhysRevB.88.235128	journal	December 2013
Reproducibility in density functional theory calculations of solids Lejaeghere, K.; Bihlmayer, G.; Bjorkman, T. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aad3000	journal	March 2016
Phonon and magnetic structure in δ-plutonium from density-functional theory Söderlind, Per; Zhou, F.; Landa, A. Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep15958	journal	October 2015
Theory of the crystal structures of cerium and the light actinides Soderlind, Per Advances in Physics, Vol. 47, Issue 6 https://doi.org/10.1080/000187398243492	journal	November 1998
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Computational modeling of actinide materials and complexes Söderlind, Per; Kotliar, G.; Haule, K. MRS Bulletin, Vol. 35, Issue 11 https://doi.org/10.1557/mrs2010.715	journal	November 2010
Effective Coulomb interaction in actinides from linear response approach Qiu, Ruizhi; Ao, Bingyun; Huang, Li Computational Materials Science, Vol. 171 https://doi.org/10.1016/j.commatsci.2019.109270	journal	January 2020
First-principles study of electronic and magnetic structure of alpha-Pu, delta-Pu, americium, and curium Kutepov, A. L.; Kutepova, S. G. Journal of Magnetism and Magnetic Materials, Vol. 272-276 https://doi.org/10.1016/j.jmmm.2003.12.706	journal	May 2004
Ab initio full charge-density study of the atomic volume of α-phase Fr, Ra, Ac, Th, Pa, U, Np, and Pu Vitos, L.; Kollár, J.; Skriver, H. L. Physical Review B, Vol. 55, Issue 8 https://doi.org/10.1103/PhysRevB.55.4947	journal	February 1997
Dilatation et pouvoir thermoelectrique du plutonium α a basse temperature Lallement, R. Journal of Physics and Chemistry of Solids, Vol. 24, Issue 12 https://doi.org/10.1016/0022-3697(63)90105-7	journal	December 1963
First-principles thermodynamic calculations for δ-Pu and ε-Pu Wang, Yi; Sun, Yunfeng Journal of Physics: Condensed Matter, Vol. 12, Issue 21 https://doi.org/10.1088/0953-8984/12/21/101	journal	May 2000
Crystal-structure stabilities and electronic structure for the light actinides Th, Pa, and U Wills, J. M.; Eriksson, Olle Physical Review B, Vol. 45, Issue 24 https://doi.org/10.1103/PhysRevB.45.13879	journal	June 1992
Elastic properties of the light actinides at high pressure Bouchet, J.; Albers, R. C. Journal of Physics: Condensed Matter, Vol. 23, Issue 21 https://doi.org/10.1088/0953-8984/23/21/215402	journal	May 2011
Structural properties of plutonium from first-principles theory Söderlind, Per; Wills, J. M.; Johansson, B. Physical Review B, Vol. 55, Issue 4 https://doi.org/10.1103/PhysRevB.55.1997	journal	January 1997
Density-functional theory for plutonium Söderlind, Per; Landa, A.; Sadigh, B. Advances in Physics, Vol. 68, Issue 1 https://doi.org/10.1080/00018732.2019.1599554	journal	January 2019
Implementation of the projector augmented-wave LDA+U method: Application to the electronic structure of NiO Bengone, O.; Alouani, M.; Blöchl, P. Physical Review B, Vol. 62, Issue 24 https://doi.org/10.1103/PhysRevB.62.16392	journal	December 2000
First-principles study of structural, elastic, electronic, vibrational and thermodynamic properties of uranium aluminides Mei, Zhi-Gang; Yacout, Abdellatif M. Computational Materials Science, Vol. 158 https://doi.org/10.1016/j.commatsci.2018.11.008	journal	February 2019
Structural, electronic, and elastic properties of equiatomic UZr alloys from first-principles Zhang, Cheng-Bin; Li, Xiu-Ping; Li, Wei-Dong Journal of Nuclear Materials, Vol. 496 https://doi.org/10.1016/j.jnucmat.2017.09.028	journal	December 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Lattice dynamics and thermodynamics of light actinides Bouchet, J.; Jomard, G. Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.014	journal	October 2007
Evaluation of first-principles techniques for obtaining materials parameters of $α$ -uranium and the (001) $α$ -uranium surface Taylor, Christopher D. Physical Review B, Vol. 77, Issue 9 https://doi.org/10.1103/PhysRevB.77.094119	journal	March 2008
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Ambient pressure phase diagram of plutonium: A unified theory for α-Pu and δ-Pu Söderlind, P. Europhysics Letters (EPL), Vol. 55, Issue 4 https://doi.org/10.1209/epl/i2001-00447-3	journal	August 2001
Phonon density of states for α-plutonium from density-functional theory Söderlind, Per; Yang, Lin H. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-55343-z	journal	December 2019
Electronic structure of fcc Th: Spin-orbit calculation with ${6 p}_{1 / 2}$ local orbital extension Kuneš, J.; Novák, P.; Schmid, R. Physical Review B, Vol. 64, Issue 15 https://doi.org/10.1103/PhysRevB.64.153102	journal	September 2001
First-principles study of surface properties of crystalline and amorphous uranium aluminides Mei, Zhi-Gang; Yacout, Abdellatif M. Applied Surface Science, Vol. 502 https://doi.org/10.1016/j.apsusc.2019.144132	journal	February 2020
Relativistic effects on the thermal expansion of the actinide elements Söderlind, Per; Nordström, Lars Physical Review B, Vol. 42, Issue 7 https://doi.org/10.1103/PhysRevB.42.4544	journal	September 1990
Pressure-induced modification of the electron structure of metallic thorium Lukoyanov, A. V.; Zaminev, M. O.; Anisimov, V. I. Journal of Experimental and Theoretical Physics, Vol. 118, Issue 1 https://doi.org/10.1134/S1063776114010105	journal	January 2014
Lattice dynamics of $α$ uranium Bouchet, J. Physical Review B, Vol. 77, Issue 2 https://doi.org/10.1103/PhysRevB.77.024113	journal	January 2008
Calculated equilibrium properties, electronic structures and structural stabilities of Th, Pa, U, Np and Pu Pénicaud, M. Journal of Physics: Condensed Matter, Vol. 12, Issue 27 https://doi.org/10.1088/0953-8984/12/27/301	journal	June 2000
Electron correlation and relativity of the 5f electrons in the U–Zr alloy system Söderlind, P.; Sadigh, B.; Lordi, V. Journal of Nuclear Materials, Vol. 444, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2013.10.021	journal	January 2014
Spin-orbit coupling in the actinide elements: A critical evaluation of theoretical equilibrium volumes Nordström, L.; Wills, J. M.; Andersson, P. H. Physical Review B, Vol. 63, Issue 3 https://doi.org/10.1103/PhysRevB.63.035103	journal	December 2000

Similar Records

NbTa_BCC_SolidSolution_128atoms_VASP6

Dataset · Tue Dec 05 00:00:00 EST 2023 · OSTI ID:1579488

Lupo Pasini, Massimiliano; Samolyuk, German; Eisenbach, Markus; +3 more

TaV_BCC_SolidSolution_128atoms_VASP6

Dataset · Fri Dec 29 00:00:00 EST 2023 · OSTI ID:1579488

Lupo Pasini, Massimiliano; Samolyuk, German; Eisenbach, Markus; +3 more

NbV_BCC_SolidSolution_128atoms_VASP6

Dataset · Wed Dec 13 00:00:00 EST 2023 · OSTI ID:1579488

Lupo Pasini, Massimiliano; Samolyuk, German; Eisenbach, Markus; +3 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
density functional theory
actinide elements
spin-orbit interaction
electron correlation
Physics - Condensed matter physics

Title: Assessing Relativistic Effects and Electron Correlation in the Actinide Metals Th to Pu

Citation Formats

References (52)

Similar Records

Related Subjects