Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U
Abstract
Correlated materials with open-shell d- and f-ions having degenerate band edge states show a rich variety of interesting properties ranging from metal-insulator transition to unconventional superconductivity. The textbook view for the electronic structure of these materials is that mean-field approaches are inappropriate, as the interelectronic interaction U is required to open a band gap between the occupied and unoccupied degenerate states while retaining symmetry. We show that the latter scenario often defining what Mott insulators are, is in fact not needed for the 3d binary oxides MnO, FeO, CoO, and NiO. The mean-field-like band theory can indeed lift such degeneracies in the binaries when nontrivial unit cell representations (polymorphous networks) are allowed to break symmetries, in conjunction with a recently developed non-empirical exchange and correlation density-functional without an on-site interelectronic interaction U. We explain how density-functional theory (DFT) in the polymorphous representation achieves band gap opening in correlated materials through a separate mechanism to the Mott-Hubbard approach. Here, we show the method predicts magnetic moments and gaps for the four binary monoxides in both the antiferromagnetic and paramagnetic phases, offering an effective alternative to symmetry-conserving approaches for studying a range of functionalities in open d- and f-shell complex materials.
- Authors:
-
- Tulane Univ., New Orleans, LA (United States); Southern Univ. of Science and Technology of China, Shenzhen (China)
- Tulane Univ., New Orleans, LA (United States)
- Univ. of Colorado, Boulder, CO (United States)
- Publication Date:
- Research Org.:
- Tulane Univ., New Orleans, LA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1737427
- Grant/Contract Number:
- SC0019350; DMR-1724791
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review. B
- Additional Journal Information:
- Journal Volume: 102; Journal Issue: 4; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Edge states; First-principles calculations; Strongly correlated systems; Bloch wave theory; Density functional theory
Citation Formats
Zhang, Yubo, Furness, James, Zhang, Ruiqi, Wang, Zhi, Zunger, Alex, and Sun, Jianwei. Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U. United States: N. p., 2020.
Web. doi:10.1103/physrevb.102.045112.
Zhang, Yubo, Furness, James, Zhang, Ruiqi, Wang, Zhi, Zunger, Alex, & Sun, Jianwei. Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U. United States. https://doi.org/10.1103/physrevb.102.045112
Zhang, Yubo, Furness, James, Zhang, Ruiqi, Wang, Zhi, Zunger, Alex, and Sun, Jianwei. Wed .
"Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U". United States. https://doi.org/10.1103/physrevb.102.045112. https://www.osti.gov/servlets/purl/1737427.
@article{osti_1737427,
title = {Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U},
author = {Zhang, Yubo and Furness, James and Zhang, Ruiqi and Wang, Zhi and Zunger, Alex and Sun, Jianwei},
abstractNote = {Correlated materials with open-shell d- and f-ions having degenerate band edge states show a rich variety of interesting properties ranging from metal-insulator transition to unconventional superconductivity. The textbook view for the electronic structure of these materials is that mean-field approaches are inappropriate, as the interelectronic interaction U is required to open a band gap between the occupied and unoccupied degenerate states while retaining symmetry. We show that the latter scenario often defining what Mott insulators are, is in fact not needed for the 3d binary oxides MnO, FeO, CoO, and NiO. The mean-field-like band theory can indeed lift such degeneracies in the binaries when nontrivial unit cell representations (polymorphous networks) are allowed to break symmetries, in conjunction with a recently developed non-empirical exchange and correlation density-functional without an on-site interelectronic interaction U. We explain how density-functional theory (DFT) in the polymorphous representation achieves band gap opening in correlated materials through a separate mechanism to the Mott-Hubbard approach. Here, we show the method predicts magnetic moments and gaps for the four binary monoxides in both the antiferromagnetic and paramagnetic phases, offering an effective alternative to symmetry-conserving approaches for studying a range of functionalities in open d- and f-shell complex materials.},
doi = {10.1103/physrevb.102.045112},
journal = {Physical Review. B},
number = 4,
volume = 102,
place = {United States},
year = {Wed Jul 08 00:00:00 EDT 2020},
month = {Wed Jul 08 00:00:00 EDT 2020}
}
Works referenced in this record:
Electronic structure of CoO, Li-doped CoO, and
journal, September 1991
- van Elp, J.; Wieland, J. L.; Eskes, H.
- Physical Review B, Vol. 44, Issue 12
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Ground- and excited-state properties of LiF in the local-density formalism
journal, September 1977
- Zunger, Alex; Freeman, A. J.
- Physical Review B, Vol. 16, Issue 6
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Electronic properties of random alloys: Special quasirandom structures
journal, November 1990
- Wei, S. -H.; Ferreira, L. G.; Bernard, James E.
- Physical Review B, Vol. 42, Issue 15
Fractional charge perspective on the band gap in density-functional theory
journal, March 2008
- Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
- Physical Review B, Vol. 77, Issue 11
Competing stripe and magnetic phases in the cuprates from first principles
journal, December 2019
- Zhang, Yubo; Lane, Christopher; Furness, James W.
- Proceedings of the National Academy of Sciences, Vol. 117, Issue 1
Nonlocal density functionals and the linear response of the homogeneous electron gas
journal, March 1998
- Mazin, I. I.; Singh, D. J.
- Physical Review B, Vol. 57, Issue 12
Magnetic Effects and the Hartree-Fock Equation
journal, May 1951
- Slater, J. C.
- Physical Review, Vol. 82, Issue 4
Density Matrix Embedding: A Simple Alternative to Dynamical Mean-Field Theory
journal, November 2012
- Knizia, Gerald; Chan, Garnet Kin-Lic
- Physical Review Letters, Vol. 109, Issue 18
Optical Absorption of CoO and MnO above and below the Néel Temperature
journal, October 1959
- Pratt, G. W.; Coelho, Roland
- Physical Review, Vol. 116, Issue 2
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Crystalline and magnetic anisotropy of the 3 -transition metal monoxides MnO, FeO, CoO, and NiO
journal, September 2012
- Schrön, A.; Rödl, C.; Bechstedt, F.
- Physical Review B, Vol. 86, Issue 11
Bond disproportionation, charge self-regulation, and ligand holes in and in -electron perovskites by density functional theory
journal, August 2018
- Dalpian, G. M.; Liu, Q.; Varignon, J.
- Physical Review B, Vol. 98, Issue 7
Magnetic collapse and the behavior of transition metal oxides at high pressure
journal, October 2016
- Leonov, I.; Pourovskii, L.; Georges, A.
- Physical Review B, Vol. 94, Issue 15
Orbital polarization and the insulating gap in the transition-metal oxides
journal, March 1990
- Norman, M. R.
- Physical Review Letters, Vol. 64, Issue 10
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995
- Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J.
- Physical Review B, Vol. 52, Issue 8
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
Understanding band gaps of solids in generalized Kohn–Sham theory
journal, March 2017
- Perdew, John P.; Yang, Weitao; Burke, Kieron
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 11
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy
journal, December 1982
- Perdew, John P.; Parr, Robert G.; Levy, Mel
- Physical Review Letters, Vol. 49, Issue 23
Inverse-photoemission measurement of iron oxides on polycrystalline Fe
journal, June 1990
- Kim, Bong-soo; Hong, Sayong; Lynch, David W.
- Physical Review B, Vol. 41, Issue 17
Equivalent type-II magnetic structures: CoO, a collinear antiferromagnet
journal, May 1978
- Herrmann-Ronzaud, D.; Burlet, P.; Rossat-Mignod, J.
- Journal of Physics C: Solid State Physics, Vol. 11, Issue 10
An accurate first-principles treatment of doping-dependent electronic structure of high-temperature cuprate superconductors
journal, March 2018
- Furness, James W.; Zhang, Yubo; Lane, Christopher
- Communications Physics, Vol. 1, Issue 1
Dynamical Singlets and Correlation-Assisted Peierls Transition in
journal, January 2005
- Biermann, S.; Poteryaev, A.; Lichtenstein, A. I.
- Physical Review Letters, Vol. 94, Issue 2
Crystal-field polarization and the insulating gap in FeO, CoO, NiO, and
journal, July 1991
- Norman, M. R.
- Physical Review B, Vol. 44, Issue 3
Electronic structure of random As alloys: Test of the ‘‘special-quasirandom-structures’’ description
journal, August 1990
- Hass, K. C.; Davis, L. C.; Zunger, Alex
- Physical Review B, Vol. 42, Issue 6
Spectrum for Nonmagnetic Mott Insulators from Power Functional within Reduced Density Matrix Functional Theory
journal, September 2015
- Shinohara, Y.; Sharma, S.; Shallcross, S.
- Journal of Chemical Theory and Computation, Vol. 11, Issue 10
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional
journal, June 2016
- Sun, Jianwei; Remsing, Richard C.; Zhang, Yubo
- Nature Chemistry, Vol. 8, Issue 9
On the Farsightedness (hyperopia) of the Standard k � p Model
journal, April 2002
- Zunger, Alex
- physica status solidi (a), Vol. 190, Issue 2
Density functionals that are one- and two- are not always many-electron self-interaction-free, as shown for H2+, He2+, LiH+, and Ne2+
journal, March 2007
- Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I.
- The Journal of Chemical Physics, Vol. 126, Issue 10
Antiferromagnetic ground state of : A parameter-free ab initio description
journal, September 2018
- Lane, Christopher; Furness, James W.; Buda, Ioana Gianina
- Physical Review B, Vol. 98, Issue 12
Effects of atomic short-range order on the electronic and optical properties of GaAsN, GaInN, and GaInAs alloys
journal, February 1998
- Bellaiche, L.; Zunger, Alex
- Physical Review B, Vol. 57, Issue 8
Efficient stochastic generation of special quasirandom structures
journal, September 2013
- van de Walle, A.; Tiwary, P.; de Jong, M.
- Calphad, Vol. 42
Magnetic ordering and exchange effects in the antiferromagnetic solid solutions
journal, June 1983
- Cheetham, A. K.; Hope, D. A. O.
- Physical Review B, Vol. 27, Issue 11
Linear response approach to the calculation of the effective interaction parameters in the method
journal, January 2005
- Cococcioni, Matteo; de Gironcoli, Stefano
- Physical Review B, Vol. 71, Issue 3
Electronic structure of metallic ferromagnets above the Curie temperature
journal, June 1985
- Staunton, J.; Gyorffy, B. L.; Pindor, A. J.
- Journal of Physics F: Metal Physics, Vol. 15, Issue 6
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
- Weigend, Florian; Ahlrichs, Reinhart
- Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
Origins versus fingerprints of the Jahn-Teller effect in -electron perovskites
journal, November 2019
- Varignon, Julien; Bibes, Manuel; Zunger, Alex
- Physical Review Research, Vol. 1, Issue 3
Complete Solution of the Korringa-Kohn-Rostoker Coherent-Potential-Approximation Equations: Cu-Ni Alloys
journal, July 1978
- Stocks, G. M.; Temmerman, W. M.; Gyorffy, B. L.
- Physical Review Letters, Vol. 41, Issue 5
Toward a predictive theory of correlated materials
journal, July 2018
- Kent, Paul R. C.; Kotliar, Gabriel
- Science, Vol. 361, Issue 6400
Insulating gap in FeO: Correlations and covalency
journal, May 1997
- Mazin, I. I.; Anisimov, V. I.
- Physical Review B, Vol. 55, Issue 19, p. 12822-12825
Polymorphous band structure model of gapping in the antiferromagnetic and paramagnetic phases of the Mott insulators MnO, FeO, CoO, and NiO
journal, January 2018
- Trimarchi, Giancarlo; Wang, Zhi; Zunger, Alex
- Physical Review B, Vol. 97, Issue 3
Electronic structure of MnO
journal, July 1991
- van Elp, J.; Potze, R. H.; Eskes, H.
- Physical Review B, Vol. 44, Issue 4
Onset of magnetic order in strongly-correlated systems from ab initio electronic structure calculations: application to transition metal oxides
journal, June 2008
- Hughes, I. D.; Däne, M.; Ernst, A.
- New Journal of Physics, Vol. 10, Issue 6
Local correlations and hole doping in NiO: A dynamical mean-field study
journal, April 2007
- Kuneš, J.; Anisimov, V. I.; Lukoyanov, A. V.
- Physical Review B, Vol. 75, Issue 16
Site-Selective Mott Transition in Rare-Earth-Element Nickelates
journal, October 2012
- Park, Hyowon; Millis, Andrew J.; Marianetti, Chris A.
- Physical Review Letters, Vol. 109, Issue 15
Effect of antiferromagnetic transition on the optical-absorption edge in MnO, , and CoO
journal, August 1974
- Chou, H-h.; Fan, H. Y.
- Physical Review B, Vol. 10, Issue 3
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Self-consistent meta-generalized gradient approximation within the projector-augmented-wave method
journal, July 2011
- Sun, Jianwei; Marsman, Martijn; Csonka, Gábor I.
- Physical Review B, Vol. 84, Issue 3
On the Crystallographic and Magnetic Structures of Nearly Stoichiometric Iron Monoxide
journal, June 1996
- Fjellvåg, Helmer; Grønvold, Fredrik; Stølen, Svein
- Journal of Solid State Chemistry, Vol. 124, Issue 1
Localization and Delocalization Errors in Density Functional Theory and Implications for Band-Gap Prediction
journal, April 2008
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- Physical Review Letters, Vol. 100, Issue 14
Discontinuous Nature of the Exchange-Correlation Functional in Strongly Correlated Systems
journal, February 2009
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- Physical Review Letters, Vol. 102, Issue 6
Magnetic Structures of MnO, FeO, CoO, and NiO
journal, June 1958
- Roth, W. L.
- Physical Review, Vol. 110, Issue 6
Many-electron self-interaction error in approximate density functionals
journal, November 2006
- Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao
- The Journal of Chemical Physics, Vol. 125, Issue 20
The alloy theoretic automated toolkit: A user guide
journal, December 2002
- van de Walle, A.; Asta, M.; Ceder, G.
- Calphad, Vol. 26, Issue 4
Projected coupled cluster theory: Optimization of cluster amplitudes in the presence of symmetry projection
journal, October 2018
- Qiu, Yiheng; Henderson, Thomas M.; Zhao, Jinmo
- The Journal of Chemical Physics, Vol. 149, Issue 16
Electrical and optical properties of FeO
journal, January 1975
- Bowen, H. K.; Adler, D.; Auker, B. H.
- Journal of Solid State Chemistry, Vol. 12, Issue 3-4, p. 355-359
Band-structure description of Mott insulators (NiO, MnO, FeO, CoO)
journal, April 1990
- Anisimov, V. I.; Korotin, M. A.; Kurmaev, E. Z.
- Journal of Physics: Condensed Matter, Vol. 2, Issue 17, p. 3973-3987
Calculating properties with the coherent-potential approximation
journal, April 1980
- Faulkner, J. S.; Stocks, G. M.
- Physical Review B, Vol. 21, Issue 8
Stretched or noded orbital densities and self-interaction correction in density functional theory
journal, May 2019
- Shahi, Chandra; Bhattarai, Puskar; Wagle, Kamal
- The Journal of Chemical Physics, Vol. 150, Issue 17
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
Special quasirandom structures
journal, July 1990
- Zunger, Alex; Wei, S.-H.; Ferreira, L. G.
- Physical Review Letters, Vol. 65, Issue 3, p. 353-356
Electronic structure of calcium hexaboride within the weighted density approximation
journal, May 2004
- Wu, Zhigang; Singh, D. J.; Cohen, R. E.
- Physical Review B, Vol. 69, Issue 19
Photoemission and inverse photoemission spectroscopy of NiO
journal, December 1984
- Hüfner, S.; Osterwalder, J.; Riesterer, T.
- Solid State Communications, Vol. 52, Issue 9
Magnitude and Origin of the Band Gap in NiO
journal, December 1984
- Sawatzky, G. A.; Allen, J. W.
- Physical Review Letters, Vol. 53, Issue 24
Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981
- Perdew, J. P.; Zunger, Alex
- Physical Review B, Vol. 23, Issue 10, p. 5048-5079
Hall mobility of photoelectrons in MnO
journal, January 1977
- Usami, Tashiro; Masumi, Taizo
- Physica B+C, Vol. 86-88
The Normal Constants of Motion in Quantum Mechanics Treated by Projection Technique
journal, July 1962
- Löwdin, Per-Olov
- Reviews of Modern Physics, Vol. 34, Issue 3
Band structure of functional oxides by screened exchange and the weighted density approximation
journal, July 2006
- Robertson, J.; Xiong, K.; Clark, S. J.
- physica status solidi (b), Vol. 243, Issue 9
Transition-Metal Monoxides: Band or Mott Insulators
journal, May 1984
- Terakura, K.; Williams, A. R.; Oguchi, T.
- Physical Review Letters, Vol. 52, Issue 20
Mott gapping in perovskites without Mott-Hubbard interelectronic repulsion energy U
journal, July 2019
- Varignon, Julien; Bibes, Manuel; Zunger, Alex
- Physical Review B, Vol. 100, Issue 3
Origin of band gaps in 3d perovskite oxides
journal, April 2019
- Varignon, Julien; Bibes, Manuel; Zunger, Alex
- Nature Communications, Vol. 10, Issue 1
Electrical and optical properties of FeO
journal, January 1975
- Bowen, H. K.; Adler, D.; Auker, B. H.
- Journal of Solid State Chemistry, Vol. 12, Issue 3-4, p. 355-359
Band-structure description of Mott insulators (NiO, MnO, FeO, CoO)
journal, April 1990
- Anisimov, V. I.; Korotin, M. A.; Kurmaev, E. Z.
- Journal of Physics: Condensed Matter, Vol. 2, Issue 17, p. 3973-3987
Semi-conductors with partially and with completely filled 3 d -lattice bands
journal, August 1937
- Boer, J. H. de; Verwey, E. J. W.
- Proceedings of the Physical Society, Vol. 49, Issue 4S
Multielectron satellites and spin polarization in photoemission from Ni compounds
journal, May 1984
- Fujimori, Atsushi; Minami, Fujio; Sugano, Satoru
- Physical Review B, Vol. 29, Issue 9
Valence-band photoemission and optical absorption in nickel compounds
journal, July 1984
- Fujimori, Atsushi; Minami, Fujio
- Physical Review B, Vol. 30, Issue 2
Application of the self-interaction correction to transition-metal oxides
journal, February 1993
- Szotek, Z.; Temmerman, W. M.; Winter, H.
- Physical Review B, Vol. 47, Issue 7
computation of the electronic spectrum of NiO
journal, November 2006
- Ren, X.; Leonov, I.; Keller, G.
- Physical Review B, Vol. 74, Issue 19
Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015
- Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P.
- Physical Review Letters, Vol. 115, Issue 3
Transition-metal oxides in the self-interaction–corrected density-functional formalism
journal, August 1990
- Svane, A.; Gunnarsson, O.
- Physical Review Letters, Vol. 65, Issue 9
Exchange, Correlation, and Spin Effects in Molecular and Solid-State Theory
journal, January 1962
- Löwdin, Per-Olov
- Reviews of Modern Physics, Vol. 34, Issue 1
Toward a predictive theory of correlated materials
journal, July 2018
- Kent, Paul R. C.; Kotliar, Gabriel
- Science, Vol. 361, Issue 6400
Onset of Magnetic Order in Strongly-Correlated Systems from ab initio Electronic Structure Calculations: Application to Transition Metal Oxides
text, January 2008
- Hughes, I. D.; Daene, M.; Ernst, A.
- arXiv
Understanding Band Gaps of Solids in Generalized Kohn-Sham Theory
text, January 2016
- Perdew, John P.; Yang, Weitao; Burke, Kieron
- arXiv
A linear response approach to the calculation of the effective interaction parameters in the LDA+U method
text, January 2004
- Cococcioni, Matteo; de Gironcoli, Stefano
- arXiv