Role of magnetic and structural symmetry breaking in forming the Mott insulating gap in Nb3⁢Cl8

Xiong, Jia-Xin; Zhang, Xiuwen; Zunger, Alex

doi:10.1103/physrevb.111.155122

Role of magnetic and structural symmetry breaking in forming the Mott insulating gap in Nb₃⁢Cl₈

Journal Article · Mon Apr 14 00:00:00 EDT 2025 · Physical Review. B

DOI:https://doi.org/10.1103/physrevb.111.155122· OSTI ID:2555843

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Univ. of Colorado, Boulder, CO (United States); Renewable and Sustainable Energy Institute, University of Colorado Boulder
Univ. of Colorado, Boulder, CO (United States)

The α-phase of the gapped insulator Nb₃Cl₈ has recently emerged as the long-sought critical testing bed for examining the importance of strong interelectronic correlation vs symmetry breaking in understanding insulation of such Mott compounds. Structural symmetry breaking detected by density functional theory (DFT) energy lowering (such as dimer formation, disproportionation, or Jahn-Teller distortions) explains insulation in both d-electron Mott-like systems and in non-d-electron cases without recourse to strong correlation. Yet, in Nb₃Cl₈, structural symmetry breaking alone (viz. formation of Nb trimers) fails to explain insulation, leading instead to a partially occupied metallic flat band, in contrast with experimental observations. We examine the role of magnetic symmetry breaking, noting that Nb₃Cl₈ is an observed paramagnet (not an antiferromagnet), thus potentially carrying also short-range ordered magnetic moments. Describing the latter as a polymorphous distribution of nonzero local moments with total zero net magnetization is demonstrated to lower the DFT total energy, while gapping the system without recourse to strong correlation or long-range magnetic order. This suggests that degeneracy removal by symmetry breaking in mean-field-like approaches—either structural, or magnetic, or both—can reduce or eliminate the need for strong correlation, allowing the use of DFT for such Mott systems.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States); Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Institute (RSEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0010467

OSTI ID:: 2555843

Alternate ID(s):: OSTI ID: 2556928
OSTI ID: 3012045

Journal Information:: Physical Review. B, Journal Name: Physical Review. B Journal Issue: 15 Vol. 111; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (66)

Struktur und elektrochemische Untersuchung von Nb3Cl8 Ströbele, Markus; Glaser, Jochen; Lachgar, Abdessadek Zeitschrift für anorganische und allgemeine Chemie, Vol. 627, Issue 8 https://doi.org/10.1002/1521-3749(200108)627:8%3C2002::AID-ZAAC2002%3E3.0.CO;2-C	journal	August 2001
Many-electron multiplet effects in the optical spectra of NiO, CoO and MnO Fazzio, A.; Zunger, Alex Solid State Communications, Vol. 52, Issue 3 https://doi.org/10.1016/0038-1098(84)90822-6	journal	October 1984
The “disordered local moment” picture of itinerant magnetism at finite temperatures Staunton, J.; Gyorffy, B. L.; Pindor, A. J. Journal of Magnetism and Magnetic Materials, Vol. 45, Issue 1 https://doi.org/10.1016/0304-8853(84)90367-6	journal	November 1984
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Efficient stochastic generation of special quasirandom structures van de Walle, A.; Tiwary, P.; de Jong, M. Calphad, Vol. 42 https://doi.org/10.1016/j.calphad.2013.06.006	journal	September 2013
Effect of static local distortions vs. dynamic motions on the stability and band gaps of cubic oxide and halide perovskites Zhao, Xin-Gang; Wang, Zhi; Malyi, Oleksandr I. Materials Today, Vol. 49 https://doi.org/10.1016/j.mattod.2021.05.021	journal	October 2021
Magnetic–Nonmagnetic Phase Transition with Interlayer Charge Disproportionation of Nb ₃ Trimers in the Cluster Compound Nb ₃ Cl ₈ Haraguchi, Yuya; Michioka, Chishiro; Ishikawa, Manabu Inorganic Chemistry, Vol. 56, Issue 6 https://doi.org/10.1021/acs.inorgchem.6b03028	journal	February 2017
Tunable Magnetic Transition to a Singlet Ground State in a 2D van der Waals Layered Trimerized Kagomé Magnet Pasco, Christopher M.; El Baggari, Ismail; Bianco, Elisabeth ACS Nano, Vol. 13, Issue 8 https://doi.org/10.1021/acsnano.9b04392	journal	July 2019
Unconventional superconductivity in magic-angle graphene superlattices Cao, Yuan; Fatemi, Valla; Fang, Shiang Nature, Vol. 556, Issue 7699 https://doi.org/10.1038/nature26160	journal	March 2018
Origin of band gaps in 3d perovskite oxides Varignon, Julien; Bibes, Manuel; Zunger, Alex Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09698-6	journal	April 2019
Identifying the ground state structures of point defects in solids Mosquera-Lois, Irea; Kavanagh, Seán R.; Walsh, Aron npj Computational Materials, Vol. 9, Issue 1 https://doi.org/10.1038/s41524-023-00973-1	journal	February 2023
Origin of superconductivity in hole doped SrBiO3 bismuth oxide perovskite from parameter-free first-principles simulations Varignon, Julien npj Computational Materials, Vol. 9, Issue 1 https://doi.org/10.1038/s41524-023-00978-w	journal	March 2023
Hidden magnetism and split off flat bands in the insulator metal transition in VO2 Zhang, Xiuwen; Xiong, Jia-Xin; Zunger, Alex npj Computational Materials, Vol. 10, Issue 1 https://doi.org/10.1038/s41524-024-01382-8	journal	September 2024
Nb3Cl8: a prototypical layered Mott-Hubbard insulator Grytsiuk, Sergii; Katsnelson, Mikhail I.; Loon, Erik G. C. P. van npj Quantum Materials, Vol. 9, Issue 1 https://doi.org/10.1038/s41535-024-00619-5	journal	January 2024
Exploration of new ferromagnetic, semiconducting and biocompatible Nb ₃ X ₈ (X = Cl, Br or I) monolayers with considerable visible and infrared light absorption Jiang, Junke; Liang, Qiuhua; Meng, Ruishen Nanoscale, Vol. 9, Issue 9 https://doi.org/10.1039/C6NR07231C	journal	January 2017
Rearrangement of van der Waals stacking and formation of a singlet state at T = 90 K in a cluster magnet Sheckelton, John P.; Plumb, Kemp W.; Trump, Benjamin A. Inorganic Chemistry Frontiers, Vol. 4, Issue 3 https://doi.org/10.1039/C6QI00470A	journal	January 2017
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Strongly Correlated Materials: Insights From Dynamical Mean-Field Theory Kotliar, Gabriel; Vollhardt, Dieter Physics Today, Vol. 57, Issue 3 https://doi.org/10.1063/1.1712502	journal	March 2004
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
False metals, real insulators, and degenerate gapped metals Malyi, Oleksandr I.; Zunger, Alex Applied Physics Reviews, Vol. 7, Issue 4 https://doi.org/10.1063/5.0015322	journal	December 2020
Short-range-order types in binary alloys: a reflection of coherent phase stability Wolverton, C.; Ozolins, V.; Zunger, Alex Journal of Physics: Condensed Matter, Vol. 12, Issue 12 https://doi.org/10.1088/0953-8984/12/12/314	journal	March 2000
How chemistry controls electron localization in 3d ¹ perovskites: a Wannier-function study Pavarini, E.; Yamasaki, A.; Nuss, J. New Journal of Physics, Vol. 7 https://doi.org/10.1088/1367-2630/7/1/188	journal	January 2005
Stability of polyatomic molecules in degenerate electronic states - I—Orbital degeneracy Jahn, H. A.; Teller, E. Proceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, Vol. 161, Issue 905, p. 220-235 https://doi.org/10.1098/rspa.1937.0142	journal	July 1937
Electron correlations in narrow energy bands Hubbard, J. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 276, Issue 1365, p. 238-257 https://doi.org/10.1098/rspa.1963.0204	journal	November 1963
New Approach to the Theory of Superexchange Interactions Anderson, P. W. Physical Review, Vol. 115, Issue 1 https://doi.org/10.1103/PhysRev.115.2	journal	July 1959
Direct Cation- -Cation Interactions in Several Oxides Goodenough, John B. Physical Review, Vol. 117, Issue 6 https://doi.org/10.1103/PhysRev.117.1442	journal	March 1960
Radiative Lifetimes of uv Multiplets in Boron, Carbon, and Nitrogen Lawrence, G. M.; Savage, Blair D. Physical Review, Vol. 141, Issue 1 https://doi.org/10.1103/PhysRev.141.67	journal	January 1966
Magnetic Effects and the Hartree-Fock Equation Slater, J. C. Physical Review, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRev.82.538	journal	May 1951
DFT + DMFT calculations of the complex band and tunneling behavior for the transition metal monoxides MnO, FeO, CoO, and NiO Zhang, Long; Staar, Peter; Kozhevnikov, Anton Physical Review B, Vol. 100, Issue 3 https://doi.org/10.1103/PhysRevB.100.035104	journal	July 2019
Symmetry-breaking polymorphous descriptions for correlated materials without interelectronic U Zhang, Yubo; Furness, James; Zhang, Ruiqi Physical Review B, Vol. 102, Issue 4 https://doi.org/10.1103/PhysRevB.102.045112	journal	July 2020
Understanding electronic peculiarities in tetragonal FeSe as local structural symmetry breaking Wang, Zhi; Zhao, Xin-Gang; Koch, Robert Physical Review B, Vol. 102, Issue 23 https://doi.org/10.1103/PhysRevB.102.235121	journal	December 2020
Mass enhancement in 3 d and s − p perovskites from symmetry breaking Wang, Zhi; Malyi, Oleksandr I.; Zhao, Xingang Physical Review B, Vol. 103, Issue 16 https://doi.org/10.1103/PhysRevB.103.165110	journal	April 2021
Intrinsic local symmetry breaking in nominally cubic paraelectric BaTiO3 Zhao, Xin-Gang; Malyi, Oleksandr I.; Billinge, Simon J. L. Physical Review B, Vol. 105, Issue 22 https://doi.org/10.1103/PhysRevB.105.224108	journal	June 2022
Symmetry breaking forms split-off flat bands in quantum oxides controlling metal versus insulator phases Xiong, Jia-Xin; Zhang, Xiuwen; Zunger, Alex Physical Review B, Vol. 111, Issue 3 https://doi.org/10.1103/PhysRevB.111.035154	journal	January 2025
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism Gunnarsson, O.; Lundqvist, B. I. Physical Review B, Vol. 13, Issue 10 https://doi.org/10.1103/PhysRevB.13.4274	journal	May 1976
Self-interaction correction to density-functional approximations for many-electron systems Perdew, J. P.; Zunger, Alex Physical Review B, Vol. 23, Issue 10, p. 5048-5079 https://doi.org/10.1103/PhysRevB.23.5048	journal	May 1981
Electronic properties of random alloys: Special quasirandom structures Wei, S. -H.; Ferreira, L. G.; Bernard, James E. Physical Review B, Vol. 42, Issue 15 https://doi.org/10.1103/PhysRevB.42.9622	journal	November 1990
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
First-principles simulated-annealing study of phase transitions and short-range order in transition-metal and semiconductor alloys Lu, Z. W.; Laks, D. B.; Wei, S. -H. Physical Review B, Vol. 50, Issue 10 https://doi.org/10.1103/PhysRevB.50.6642	journal	September 1994
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
Jahn-Teller distortion and magnetic structures in LaMnO 3 Sawada, H.; Morikawa, Y.; Terakura, K. Physical Review B, Vol. 56, Issue 19 https://doi.org/10.1103/PhysRevB.56.12154	journal	November 1997
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
Mean-Value Point in the Brillouin Zone Baldereschi, A. Physical Review B, Vol. 7, Issue 12 https://doi.org/10.1103/PhysRevB.7.5212	journal	June 1973
Full orbital calculation scheme for materials with strongly correlated electrons Anisimov, V. I.; Kondakov, D. E.; Kozhevnikov, A. V. Physical Review B, Vol. 71, Issue 12 https://doi.org/10.1103/PhysRevB.71.125119	journal	March 2005
LDA + DMFT computation of the electronic spectrum of NiO Ren, X.; Leonov, I.; Keller, G. Physical Review B, Vol. 74, Issue 19 https://doi.org/10.1103/PhysRevB.74.195114	journal	November 2006
Special Points in the Brillouin Zone Chadi, D. J.; Cohen, Marvin L. Physical Review B, Vol. 8, Issue 12 https://doi.org/10.1103/PhysRevB.8.5747	journal	December 1973
Quantifying electronic correlation strength in a complex oxide: A combined DMFT and ARPES study of LaNiO 3 Nowadnick, E. A.; Ruf, J. P.; Park, H. Physical Review B, Vol. 92, Issue 24 https://doi.org/10.1103/PhysRevB.92.245109	journal	December 2015
Identifying multiexcitons inMoS2monolayers at room temperature Lee, Hyun Seok; Kim, Min Su; Kim, Hyun Physical Review B, Vol. 93, Issue 14 https://doi.org/10.1103/PhysRevB.93.140409	journal	April 2016
Twistronics: Manipulating the electronic properties of two-dimensional layered structures through their twist angle Carr, Stephen; Massatt, Daniel; Fang, Shiang Physical Review B, Vol. 95, Issue 7 https://doi.org/10.1103/PhysRevB.95.075420	journal	February 2017
Polymorphous band structure model of gapping in the antiferromagnetic and paramagnetic phases of the Mott insulators MnO, FeO, CoO, and NiO Trimarchi, Giancarlo; Wang, Zhi; Zunger, Alex Physical Review B, Vol. 97, Issue 3 https://doi.org/10.1103/PhysRevB.97.035107	journal	January 2018
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
New Technique for Investigating Noncrystalline Structures: Fourier Analysis of the Extended X-Ray—Absorption Fine Structure Sayers, Dale E.; Stern, Edward A.; Lytle, Farrel W. Physical Review Letters, Vol. 27, Issue 18 https://doi.org/10.1103/PhysRevLett.27.1204	journal	November 1971
Electric Field Breakdown of Charge-Density-Wave—Induced Anomalies in Nb Se 3 Monçeau, P.; Ong, N. P.; Portis, A. M. Physical Review Letters, Vol. 37, Issue 10 https://doi.org/10.1103/PhysRevLett.37.602	journal	September 1976
Special quasirandom structures Zunger, Alex; Wei, S.-H.; Ferreira, L. G. Physical Review Letters, Vol. 65, Issue 3, p. 353-356 https://doi.org/10.1103/PhysRevLett.65.353	journal	July 1990
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
Mott Transition and Suppression of Orbital Fluctuations in Orthorhombic 3 d 1 Perovskites Pavarini, E.; Biermann, S.; Poteryaev, A. Physical Review Letters, Vol. 92, Issue 17 https://doi.org/10.1103/PhysRevLett.92.176403	journal	April 2004
Correlated local dipoles in PbTe Sangiorgio, Boris; Bozin, Emil S.; Malliakas, Christos D. Physical Review Materials, Vol. 2, Issue 8 https://doi.org/10.1103/PhysRevMaterials.2.085402	journal	August 2018
Screening two-dimensional materials with topological flat bands Liu, Hang; Meng, Sheng; Liu, Feng Physical Review Materials, Vol. 5, Issue 8 https://doi.org/10.1103/PhysRevMaterials.5.084203	journal	August 2021
Rise and fall of Mott insulating gaps in YNiO3 paramagnets as a reflection of symmetry breaking and remaking Malyi, Oleksandr I.; Zunger, Alex Physical Review Materials, Vol. 7, Issue 4 https://doi.org/10.1103/PhysRevMaterials.7.044409	journal	April 2023
Origins versus fingerprints of the Jahn-Teller effect in d -electron A B X 3 perovskites Varignon, Julien; Bibes, Manuel; Zunger, Alex Physical Review Research, Vol. 1, Issue 3 https://doi.org/10.1103/PhysRevResearch.1.033131	journal	November 2019
Discovery of a Single-Band Mott Insulator in a van der Waals Flat-Band Compound Gao, Shunye; Zhang, Shuai; Wang, Cuixiang Physical Review X, Vol. 13, Issue 4 https://doi.org/10.1103/PhysRevX.13.041049	journal	December 2023
The dynamics of charge-density waves Grüner, G. Reviews of Modern Physics, Vol. 60, Issue 4 https://doi.org/10.1103/RevModPhys.60.1129	journal	October 1988
Metal-insulator transitions Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori Reviews of Modern Physics, Vol. 70, Issue 4, p. 1039-1263 https://doi.org/10.1103/RevModPhys.70.1039	journal	October 1998
Magnetic pair distribution function analysis of local magnetic correlations Frandsen, Benjamin A.; Yang, Xiaohao; Billinge, Simon J. L. Acta Crystallographica Section A Foundations and Advances, Vol. 70, Issue 1, p. 3-11 https://doi.org/10.1107/S2053273313033081	journal	December 2013

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