Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides
Abstract
Pressure-induced structural transitions of the alkaline earth hexaborides, CaB6, SrB6, and BaB6, are studied theoretically using electron counting rules and density functional theory calculations. Here, we demonstrate the applicability of gas-phase borane electron counting methods to solid-state metal borides under pressure and validate the assumptions of the rules by density functional theory (DFT) calculations. All three compounds share ambient-pressure and high-pressure structures, but BaB6 differs from CaB6 and SrB6 at intermediate pressures. The unique BaB6 phase is shown to break electron counting rules, while all other phases obey them. This anomaly is resolved by DFT, which reveals B–Ba covalency and unusual B–B π bonding under pressure. The relationships between structure and bonding can help us to understand the exotic behavior of lanthanide hexaborides and design new borides with desirable properties. Developing electron counting procedures for solids will enhance materials discovery efforts with chemical intuition.
- Publication Date:
- Research Org.:
- Univ. of California, Los Angeles, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1968773
- Grant/Contract Number:
- SC0019152
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 61; Journal Issue: 46; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical structure; Cluster chemistry; Metals; Particulate matter; Phase transitions
Citation Formats
Morgan, Harry W. T., and Alexandrova, Anastassia N. Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides. United States: N. p., 2022.
Web. doi:10.1021/acs.inorgchem.2c03190.
Morgan, Harry W. T., & Alexandrova, Anastassia N. Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides. United States. https://doi.org/10.1021/acs.inorgchem.2c03190
Morgan, Harry W. T., and Alexandrova, Anastassia N. Wed .
"Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides". United States. https://doi.org/10.1021/acs.inorgchem.2c03190. https://www.osti.gov/servlets/purl/1968773.
@article{osti_1968773,
title = {Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides},
author = {Morgan, Harry W. T. and Alexandrova, Anastassia N.},
abstractNote = {Pressure-induced structural transitions of the alkaline earth hexaborides, CaB6, SrB6, and BaB6, are studied theoretically using electron counting rules and density functional theory calculations. Here, we demonstrate the applicability of gas-phase borane electron counting methods to solid-state metal borides under pressure and validate the assumptions of the rules by density functional theory (DFT) calculations. All three compounds share ambient-pressure and high-pressure structures, but BaB6 differs from CaB6 and SrB6 at intermediate pressures. The unique BaB6 phase is shown to break electron counting rules, while all other phases obey them. This anomaly is resolved by DFT, which reveals B–Ba covalency and unusual B–B π bonding under pressure. The relationships between structure and bonding can help us to understand the exotic behavior of lanthanide hexaborides and design new borides with desirable properties. Developing electron counting procedures for solids will enhance materials discovery efforts with chemical intuition.},
doi = {10.1021/acs.inorgchem.2c03190},
journal = {Inorganic Chemistry},
number = 46,
volume = 61,
place = {United States},
year = {Wed Nov 09 00:00:00 EST 2022},
month = {Wed Nov 09 00:00:00 EST 2022}
}
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Works referenced in this record:
The atom and the Molecule.
journal, April 1916
- Lewis, Gilbert N.
- Journal of the American Chemical Society, Vol. 38, Issue 4
The Arrangement of Electrons in Atoms and Molecules.
journal, June 1919
- Langmuir, Irving
- Journal of the American Chemical Society, Vol. 41, Issue 6
The structural significance of the number of skeletal bonding electron-pairs in carboranes, the higher boranes and borane anions, and various transition-metal carbonyl cluster compounds
journal, January 1971
- Wade, K.
- Journal of the Chemical Society D: Chemical Communications, Issue 15
A General Theory for Cluster and Ring Compounds of the Main Group and Transition Elements
journal, April 1972
- Mingos, D. M. P.
- Nature Physical Science, Vol. 236, Issue 68
Anomalous Diamagnetic Susceptibility in 13-Atom Platinum Nanocluster Superatoms
journal, March 2014
- Roduner, Emil; Jensen, Christopher; van Slageren, Joris
- Angewandte Chemie International Edition, Vol. 53, Issue 17
Electronic structure of H adsorbed on Pt13 clusters
journal, May 1997
- Watari, Noriko; Ohnishi, Shuhei
- The Journal of Chemical Physics, Vol. 106, Issue 18
Electron Counting in Solids: Oxidation States, Partial Charges, and Ionicity
journal, April 2017
- Walsh, Aron; Sokol, Alexey A.; Buckeridge, John
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 9
The Zintl-Klemm Concept - A Historical Survey: The Zintl-Klemm Concept - A Historical Survey
journal, November 2014
- Nesper, Reinhard
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 14
Generality of the 18- n Rule: Intermetallic Structural Chemistry Explained through Isolobal Analogies to Transition Metal Complexes
journal, November 2015
- Yannello, Vincent J.; Fredrickson, Daniel C.
- Inorganic Chemistry, Vol. 54, Issue 23
Exploratory Synthesis: The Fascinating and Diverse Chemistry of Polar Intermetallic Phases † † This article is based on J. D. Corbett’s address upon receipt of the 2008 American Chemical Society’s F. Albert Cotton Award in Synthetic Inorganic Chemistry sponsored by the F. Albert Cotton Endowment Fund.
journal, January 2010
- Corbett, John D.
- Inorganic Chemistry, Vol. 49, Issue 1
Chemistry under high pressure
journal, September 2020
- Miao, Maosheng; Sun, Yuanhui; Zurek, Eva
- Nature Reviews Chemistry, Vol. 4, Issue 10
The XtalOpt Evolutionary Algorithm for Crystal Structure Prediction
journal, December 2020
- Falls, Zackary; Avery, Patrick; Wang, Xiaoyu
- The Journal of Physical Chemistry C, Vol. 125, Issue 3
Structure prediction drives materials discovery
journal, April 2019
- Oganov, Artem R.; Pickard, Chris J.; Zhu, Qiang
- Nature Reviews Materials, Vol. 4, Issue 5
Crystal Structure Prediction via Efficient Sampling of the Potential Energy Surface
journal, July 2022
- Wang, Yanchao; Lv, Jian; Gao, Pengyue
- Accounts of Chemical Research, Vol. 55, Issue 15
Hardening Effects in Superhard Transition-Metal Borides
journal, December 2021
- Pangilinan, Lisa E.; Hu, Shanlin; Hamilton, Spencer G.
- Accounts of Materials Research, Vol. 3, Issue 1
A Unifying Electron-Counting Rule for Macropolyhedral Boranes, Metallaboranes, and Metallocenes
journal, May 2001
- Jemmis, Eluvathingal D.; Balakrishnarajan, Musiri M.; Pancharatna, Pattath D.
- Journal of the American Chemical Society, Vol. 123, Issue 18
Fragment approach to the electronic structure of allotrope
journal, April 2017
- Karmodak, Naiwrit; Jemmis, Eluvathingal D.
- Physical Review B, Vol. 95, Issue 16
An electron counting formula to explain and to predict hydrogenated and metallated borophenes
journal, January 2022
- Chaliha, Rinkumoni; Sravanakumar Perumalla, D.; Jemmis, Eluvathingal D.
- Chemical Communications, Vol. 58, Issue 71
Disorder–Order Structural Transformation in Electron-Poor Sr 3 Au 8 Sn 3 Driven by Chemical Bonding Optimization
journal, May 2013
- Lin, Qisheng; Vetter, Jordan; Corbett, John D.
- Inorganic Chemistry, Vol. 52, Issue 11
Structure and bonding in boron carbide: The invincibility of imperfections
journal, January 2007
- Balakrishnarajan, Musiri M.; Pancharatna, Pattath D.; Hoffmann, Roald
- New Journal of Chemistry, Vol. 31, Issue 4
Structural motifs and bonding in two families of boron structures predicted at megabar pressures
journal, May 2021
- Hilleke, Katerina P.; Ogitsu, Tadashi; Zhang, Shuai
- Physical Review Materials, Vol. 5, Issue 5
High-Pressure Evolution of Unexpected Chemical Bonding and Promising Superconducting Properties of YB 6
journal, November 2018
- Wang, Jianyun; Song, Xianqi; Shao, Xuecheng
- The Journal of Physical Chemistry C, Vol. 122, Issue 49
Magnetism and Antiferroelectricity in
journal, March 2012
- Popov, Igor; Baadji, Nadjib; Sanvito, Stefano
- Physical Review Letters, Vol. 108, Issue 10
Towards a Single Chemical Model for Understanding Lanthanide Hexaborides
journal, October 2020
- Munarriz, Julen; Robinson, Paul J.; Alexandrova, Anastassia N.
- Angewandte Chemie, Vol. 132, Issue 50
Dynamical Bonding Driving Mixed Valency in a Metal Boride
journal, April 2020
- Robinson, Paul J.; Munarriz, Julen; Valentine, Michael E.
- Angewandte Chemie, Vol. 132, Issue 27
Stability and bonding nature of clathrate H cages in a near-room-temperature superconductor
journal, February 2021
- Yi, Seho; Wang, Chongze; Jeon, Hyunsoo
- Physical Review Materials, Vol. 5, Issue 2
Superconductivity at 250 K in lanthanum hydride under high pressures
journal, May 2019
- Drozdov, A. P.; Kong, P. P.; Minkov, V. S.
- Nature, Vol. 569, Issue 7757
Hole superconductivity xOr hot hydride superconductivity
journal, November 2021
- Hirsch, J. E.
- Journal of Applied Physics, Vol. 130, Issue 18
Superconductive sodalite-like clathrate calcium hydride at high pressures
journal, April 2012
- Wang, H.; Tse, J. S.; Tanaka, K.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 17
Growth of YB6 single crystals
journal, August 1976
- Fisk, Z.; Schmidt, P. H.; Longinotti, L. D.
- Materials Research Bulletin, Vol. 11, Issue 8
Two-dimensional Fermi surfaces in Kondo insulator SmB 6
journal, December 2014
- Li, G.; Xiang, Z.; Yu, F.
- Science, Vol. 346, Issue 6214
Hexaborides: a review of structure, synthesis and processing
journal, November 2019
- Cahill, James T.; Graeve, Olivia A.
- Journal of Materials Research and Technology, Vol. 8, Issue 6
Kondo and anti-Kondo coupling to local moments in
journal, April 2004
- Kuneš, J.; Pickett, W. E.
- Physical Review B, Vol. 69, Issue 16
Pressure effects on magnetic properties and electronic structure of EuB6 and GdB6
journal, January 2012
- Grechnev, G. E.; Logosha, A. V.; Panfilov, A. S.
- Journal of Alloys and Compounds, Vol. 511, Issue 1
Pressure-induced exotic states in rare earth hexaborides
journal, July 2016
- Sun, Liling; Wu, Qi
- Reports on Progress in Physics, Vol. 79, Issue 8
Pressure-induced polymorphism in and deformation mechanisms of covalent networks
journal, December 2019
- Zhu, Li; Borstad, Gustav M.; Cohen, R. E.
- Physical Review B, Vol. 100, Issue 21
Pressure-Driven Evolution of the Covalent Network in
journal, August 2012
- Kolmogorov, A. N.; Shah, S.; Margine, E. R.
- Physical Review Letters, Vol. 109, Issue 7
The stability of B 6 octahedron in BaB 6 under high pressure
journal, January 2016
- Li, Xin; Huang, Xiaoli; Duan, Defang
- RSC Advances, Vol. 6, Issue 22
Stability and superconductivity of Ca-B phases at ambient and high pressure
journal, July 2013
- Shah, Sheena; Kolmogorov, Aleksey N.
- Physical Review B, Vol. 88, Issue 1
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Electrochemical Synthesis of Magnesium Hexaboride by Molten Salt Technique
journal, August 2014
- Angappan, S.; Kalaiselvi, N.; Sudha, R.
- International Scholarly Research Notices, Vol. 2014
Pressure Effect on the Einstein-Like Phonon Mode in Superconducting
$$\hbox {YB}_{6}$$
YB
6
journal, December 2016
- Orendáč, Mat.; Gabáni, S.; Gažo, E.
- Journal of Low Temperature Physics, Vol. 187, Issue 5-6
Phonons in YB6 and LaB6: Effects of temperature and pressure
journal, September 2015
- Ponosov, Yu. S.; Shitsevalova, N. Yu.
- JETP Letters, Vol. 102, Issue 5
Electronic Requirements for Macropolyhedral Boranes
journal, December 2001
- Jemmis, Eluvathingal D.; Balakrishnarajan, Musiri M.; Pancharatna, Pattath D.
- Chemical Reviews, Vol. 102, Issue 1
Chemistry under extreme conditions: Pressure evolution of chemical bonding and structure in dense solids
journal, January 2020
- Yoo, Choong-Shik
- Matter and Radiation at Extremes, Vol. 5, Issue 1
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
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
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993
- Dronskowski, Richard; Bloechl, Peter E.
- The Journal of Physical Chemistry, Vol. 97, Issue 33
Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets
journal, June 2011
- Deringer, Volker L.; Tchougréeff, Andrei L.; Dronskowski, Richard
- The Journal of Physical Chemistry A, Vol. 115, Issue 21
LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding
journal, February 2016
- Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
- Journal of Computational Chemistry, Vol. 37, Issue 11
Electron Requirements of Bonds in Metal Borides
journal, January 1963
- Johnson, Robert W.; Daane, A. H.
- The Journal of Chemical Physics, Vol. 38, Issue 2
Structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba)
journal, April 2015
- Cinthia, A. Jemmy; Priyanga, G. Sudha; Rajeswarapalanichamy, R.
- Journal of Physics and Chemistry of Solids, Vol. 79
Pressure-Induced Transitions in the 1-Dimensional Vanadium Oxyhydrides Sr2VO3H and Sr3V2O5H2, and Comparison to 2-Dimensional SrVO2H
journal, October 2019
- Yamamoto, Takafumi; Morgan, Harry W. T.; Zeng, Dihao
- Inorganic Chemistry, Vol. 58, Issue 22
Sequential Pressure-Induced B1–B2 Transitions in the Anion-Ordered Oxyhydride Ba2YHO3
journal, April 2022
- Morgan, Harry W. T.; Yamamoto, Takafumi; Nishikubo, Takumi
- Inorganic Chemistry, Vol. 61, Issue 18
Observation of alkaline earth complexes M(CO) 8 (M = Ca, Sr, or Ba) that mimic transition metals
journal, August 2018
- Wu, Xuan; Zhao, Lili; Jin, Jiaye
- Science, Vol. 361, Issue 6405
Transition-Metal Chemistry of the Heavier Alkaline Earth Atoms Ca, Sr, and Ba
journal, July 2021
- Zhou, Mingfei; Frenking, Gernot
- Accounts of Chemical Research, Vol. 54, Issue 15