Dynamical Bonding Driving Mixed Valency in a Metal Boride
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Institute for Quantum Matter (IQM); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1671085
- Alternate Identifier(s):
- OSTI ID: 1608371
- Report Number(s):
- LA-UR-19-30421
Journal ID: ISSN 1433-7851
- Grant/Contract Number:
- 89233218CNA000001; SC0019331
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 27; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science; chemical bonding; mixed valency; pressure induced phase transitions; Raman spectroscopy; samarium hexaboride
Citation Formats
Robinson, Paul J., Munarriz, Julen, Valentine, Michael E., Granmoe, Austin, Drichko, Natalia, Chamorro, Juan R., Rosa, Priscila F., McQueen, Tyrel M., and Alexandrova, Anastassia N. Dynamical Bonding Driving Mixed Valency in a Metal Boride. United States: N. p., 2020.
Web. doi:10.1002/anie.202000945.
Robinson, Paul J., Munarriz, Julen, Valentine, Michael E., Granmoe, Austin, Drichko, Natalia, Chamorro, Juan R., Rosa, Priscila F., McQueen, Tyrel M., & Alexandrova, Anastassia N. Dynamical Bonding Driving Mixed Valency in a Metal Boride. United States. https://doi.org/10.1002/anie.202000945
Robinson, Paul J., Munarriz, Julen, Valentine, Michael E., Granmoe, Austin, Drichko, Natalia, Chamorro, Juan R., Rosa, Priscila F., McQueen, Tyrel M., and Alexandrova, Anastassia N. Mon .
"Dynamical Bonding Driving Mixed Valency in a Metal Boride". United States. https://doi.org/10.1002/anie.202000945. https://www.osti.gov/servlets/purl/1671085.
@article{osti_1671085,
title = {Dynamical Bonding Driving Mixed Valency in a Metal Boride},
author = {Robinson, Paul J. and Munarriz, Julen and Valentine, Michael E. and Granmoe, Austin and Drichko, Natalia and Chamorro, Juan R. and Rosa, Priscila F. and McQueen, Tyrel M. and Alexandrova, Anastassia N.},
abstractNote = {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.},
doi = {10.1002/anie.202000945},
journal = {Angewandte Chemie (International Edition)},
number = 27,
volume = 59,
place = {United States},
year = {2020},
month = {4}
}
Web of Science
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