Dynamical Bonding Driving Mixed Valency in a Metal Boride

Robinson, Paul J.; Munarriz, Julen; Valentine, Michael E.; Granmoe, Austin; Drichko, Natalia; Chamorro, Juan R.; Rosa, Priscila F.; McQueen, Tyrel M.; Alexandrova, Anastassia N.

doi:10.1002/anie.202000945

Title: Dynamical Bonding Driving Mixed Valency in a Metal Boride

Journal Article · 06 April 2020 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202000945 · OSTI ID:1671085

^[1];

^[2]; Valentine, Michael E. ^[3]; Granmoe, Austin ^[3]; Drichko, Natalia ^[3]; Chamorro, Juan R. ^[3]; Rosa, Priscila F. ^[4]; McQueen, Tyrel M. ^[3];

^[2]

Univ. of California, Los Angeles, CA (United States); Columbia Univ., New York, NY (United States)
Univ. of California, Los Angeles, CA (United States)
Johns Hopkins Univ., Baltimore, MD (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Abstract Samarium hexaboride is an anomaly, having many exotic and seemingly mutually incompatible properties. It was proposed to be a mixed‐valent semiconductor, and later a topological Kondo insulator, and yet has a Fermi surface despite being an insulator. We propose a new and unified understanding of SmB ₆ centered on the hitherto unrecognized dynamical bonding effect: the coexistence of two Sm−B bonding modes within SmB ₆ , corresponding to different oxidation states of the Sm. The mixed valency arises in SmB ₆ from thermal population of these distinct minima enabled by motion of B. Our model simultaneously explains the thermal valence fluctuations, appearance of magnetic Fermi surface, excess entropy at low temperatures, pressure‐induced phase transitions, and related features in Raman spectra and their unexpected dependence on temperature and boron isotope.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Institute for Quantum Matter (IQM); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: 89233218CNA000001; SC0019331

OSTI ID:: 1671085

Alternate ID(s):: OSTI ID: 1608371

Report Number(s):: LA-UR-19-30421

Journal Information:: Angewandte Chemie (International Edition), Vol. 59, Issue 27; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Surface-dominated conduction up to 240 K in the Kondo insulator SmB6 under strain Stern, A.; Dzero, M.; Galitski, V. M. Nature Materials, Vol. 16, Issue 7 https://doi.org/10.1038/nmat4888	journal	April 2017
Temperature dependence of Sm valence in SmB ₆ studied by X-ray absorption spectroscopy Mizumaki, Masaichiro; Tsutsui, Satoshi; Iga, Fumitoshi Journal of Physics: Conference Series, Vol. 176 https://doi.org/10.1088/1742-6596/176/1/012034	journal	June 2009
Chemical Bonding of Crystalline LnB ₆ (Ln = La–Lu) and Its Relationship with Ln ₂ B ₈ Gas-Phase Complexes Li, Wan-Lu; Ertural, Christina; Bogdanovski, Dimitri Inorganic Chemistry, Vol. 57, Issue 20 https://doi.org/10.1021/acs.inorgchem.8b02263	journal	September 2018
Design of hard crystals Gilman, J. J.; Cumberland, R. W.; Kaner, R. B. International Journal of Refractory Metals and Hard Materials, Vol. 24, Issue 1-2 https://doi.org/10.1016/j.ijrmhm.2005.05.015	journal	January 2006
Two-dimensional Fermi surfaces in Kondo insulator SmB ₆ Li, G.; Xiang, Z.; Yu, F. Science, Vol. 346, Issue 6214 https://doi.org/10.1126/science.1250366	journal	December 2014
Sm B 6 : Kondo Insulator or Exotic Metal? Cooley, J. C.; Aronson, M. C.; Fisk, Z. Physical Review Letters, Vol. 74, Issue 9 https://doi.org/10.1103/PhysRevLett.74.1629	journal	February 1995
Additional energy scale in SmB6 at low-temperature Jiao, L.; Rößler, S.; Kim, D. J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13762	journal	December 2016
How Chemistry and Physics Meet in the Solid State Hoffmann, Roald Angewandte Chemie International Edition in English, Vol. 26, Issue 9 https://doi.org/10.1002/anie.198708461	journal	September 1987
Topological surface state in the Kondo insulator samarium hexaboride Kim, D. J.; Xia, J.; Fisk, Z. Nature Materials, Vol. 13, Issue 5 https://doi.org/10.1038/nmat3913	journal	March 2014
Pressure-Resistant Intermediate Valence in the Kondo Insulator SmB 6 Butch, Nicholas P.; Paglione, Johnpierre; Chow, Paul Physical Review Letters, Vol. 116, Issue 15 https://doi.org/10.1103/PhysRevLett.116.156401	journal	April 2016
Excitons in topological Kondo insulators: Theory of thermodynamic and transport anomalies in SmB 6 Knolle, Johannes; Cooper, Nigel R. Physical Review Letters, Vol. 118, Issue 9 https://doi.org/10.1103/PhysRevLett.118.096604	journal	March 2017
Unconventional Fermi surface in an insulating state Tan, B. S.; Hsu, Y. - T.; Zeng, B. Science, Vol. 349, Issue 6245 https://doi.org/10.1126/science.aaa7974	journal	July 2015
Advancements in the Search for Superhard Ultra-Incompressible Metal Borides Levine, Jonathan B.; Tolbert, Sarah H.; Kaner, Richard B. Advanced Functional Materials, Vol. 19, Issue 22 https://doi.org/10.1002/adfm.200901257	journal	November 2009
Theory of mixed valence: Metals or small gap insulators (invited) Martin, Richard M.; Allen, J. W. Journal of Applied Physics, Vol. 50, Issue B11 https://doi.org/10.1063/1.326765	journal	January 1979
Effects of Configuration Interaction on Intensities and Phase Shifts Fano, U. Physical Review, Vol. 124, Issue 6 https://doi.org/10.1103/PhysRev.124.1866	journal	December 1961
Quantum-chemical insights into mixed-valence systems: within and beyond the Robin–Day scheme Parthey, M.; Kaupp, M. Chem. Soc. Rev., Vol. 43, Issue 14 https://doi.org/10.1039/C3CS60481K	journal	January 2014
Valence transitions and intermediate valence states in rare earth and actinide materials Robinson, J. M. Physics Reports, Vol. 51, Issue 1 https://doi.org/10.1016/0370-1573(79)90070-X	journal	March 1979
Harder than diamond: Dreams and reality Brazhkin, Vadim V.; Lyapin, Alexander G.; Hemley, Russell J. Philosophical Magazine A, Vol. 82, Issue 2 https://doi.org/10.1080/01418610208239596	journal	January 2002
Study of valence mixing in SmB 6 by x-ray photoelectron spectroscopy Chazalviel, J. N.; Campagna, M.; Wertheim, G. K. Physical Review B, Vol. 14, Issue 10 https://doi.org/10.1103/PhysRevB.14.4586	journal	November 1976
Kondo Breakdown and Quantum Oscillations in SmB 6 Erten, Onur; Ghaemi, Pouyan; Coleman, Piers Physical Review Letters, Vol. 116, Issue 4 https://doi.org/10.1103/PhysRevLett.116.046403	journal	January 2016
Metal-Insulator Transitions: A Simple Theoretical Model Ramirez, Ricardo; Falicov, L. M.; Kimball, J. C. Physical Review B, Vol. 2, Issue 8 https://doi.org/10.1103/PhysRevB.2.3383	journal	October 1970
Understanding How Bonding Controls Strength Anisotropy in Hard Materials by Comparing the High-Pressure Behavior of Orthorhombic and Tetragonal Tungsten Monoboride Lei, Jialin; Yeung, Michael T.; Robinson, Paul J. The Journal of Physical Chemistry C, Vol. 122, Issue 10 https://doi.org/10.1021/acs.jpcc.7b11478	journal	February 2018
Topological Kondo Insulators Dzero, Maxim; Xia, Jing; Galitski, Victor Annual Review of Condensed Matter Physics, Vol. 7, Issue 1 https://doi.org/10.1146/annurev-conmatphys-031214-014749	journal	March 2016
The Metallic State Pauling, Linus Nature, Vol. 161, Issue 4104 https://doi.org/10.1038/1611019b0	journal	June 1948
Die Begegnung von Chemie und Physik im Festkörper Hoffmann, Roald Angewandte Chemie, Vol. 99, Issue 9 https://doi.org/10.1002/ange.19870990907	journal	September 1987
Mystery of Three Borides: Differential Metal–Boron Bonding Governing Superhard Structures Robinson, Paul J.; Liu, Gaoxiang; Ciborowski, Sandra Chemistry of Materials, Vol. 29, Issue 23 https://doi.org/10.1021/acs.chemmater.7b04378	journal	November 2017
A resonating-valence-bond theory of metals and intermetallic compounds Pauling, Linus Carl Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 196, Issue 1046, p. 343-362 https://doi.org/10.1098/rspa.1949.0032	journal	April 1949
Breakdown of the Kondo insulating state in SmB 6 by introducing Sm vacancies Valentine, Michael E.; Koohpayeh, Seyed; Phelan, W. Adam Physical Review B, Vol. 94, Issue 7 https://doi.org/10.1103/PhysRevB.94.075102	journal	August 2016
High borides: determining the features and details of lattice dynamics from neutron spectroscopy Alekseev, P. A. Physics-Uspekhi, Vol. 58, Issue 4 https://doi.org/10.3367/UFNe.0185.201504b.0353	journal	April 2015
SmB ₆ ^– Cluster Anion: Covalency Involving f Orbitals Robinson, Paul J.; Zhang, Xinxing; McQueen, Tyrel The Journal of Physical Chemistry A, Vol. 121, Issue 8 https://doi.org/10.1021/acs.jpca.7b00247	journal	February 2017
Physical Properties of Sm B 6 Nickerson, J. C.; White, R. M.; Lee, K. N. Physical Review B, Vol. 3, Issue 6 https://doi.org/10.1103/PhysRevB.3.2030	journal	March 1971
Raman scattering investigation of R B 6 ( R = Ca , La, Ce, Pr, Sm, Gd, Dy, and Yb) Ogita, Norio; Nagai, Shinji; Okamoto, Naoki Physical Review B, Vol. 68, Issue 22 https://doi.org/10.1103/PhysRevB.68.224305	journal	December 2003
Elastic, electronic and thermal properties of topological insulator SmB ₆ : first-principles calculations Li, Li; Hu, Cui-E; Tang, Mei Philosophical Magazine, Vol. 97, Issue 14 https://doi.org/10.1080/14786435.2017.1290847	journal	February 2017
Topological surface states interacting with bulk excitations in the Kondo insulator SmB ₆ revealed via planar tunneling spectroscopy Park, Wan Kyu; Sun, Lunan; Noddings, Alexander Proceedings of the National Academy of Sciences, Vol. 113, Issue 24 https://doi.org/10.1073/pnas.1606042113	journal	May 2016
Observation of possible topological in-gap surface states in the Kondo insulator SmB6 by photoemission Jiang, J.; Li, S.; Zhang, T. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms4010	journal	December 2013
Skyrme Insulators: Insulators at the Brink of Superconductivity Erten, Onur; Chang, Po-Yao; Coleman, Piers Physical Review Letters, Vol. 119, Issue 5 https://doi.org/10.1103/PhysRevLett.119.057603	journal	August 2017
Fermi surface in the absence of a Fermi liquid in the Kondo insulator SmB6 Hartstein, M.; Toews, W. H.; Hsu, Y. -T. Nature Physics, Vol. 14, Issue 2 https://doi.org/10.1038/nphys4295	journal	October 2017
The Metallic State Pauling, Linus Nature, Vol. 161, Issue 4104 https://doi.org/10.1038/1611019b0	journal	June 1948
A resonating-valence-bond theory of metals and intermetallic compounds Pauling, Linus Carl Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 196, Issue 1046, p. 343-362 https://doi.org/10.1098/rspa.1949.0032	journal	April 1949
Skyrme insulators: insulators at the brink of superconductivity Erten, Onur; Chang, Po-Yao; Coleman, Piers arXiv https://doi.org/10.48550/arxiv.1701.06582	text	January 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Material Science
chemical bonding
mixed valency
pressure induced phase transitions
Raman spectroscopy
samarium hexaboride

Title: Dynamical Bonding Driving Mixed Valency in a Metal Boride

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