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.
- Authors:
-
- Univ. of California, Los Angeles, CA (United States)
- 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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