Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides

Morgan, Harry W. T.; Alexandrova, Anastassia N.

doi:10.1021/acs.inorgchem.2c03190

Electron Counting and High-Pressure Phase Transformations in Metal Hexaborides

Journal Article · Wed Nov 09 00:00:00 EST 2022 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.2c03190· OSTI ID:1968773

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Univ. of California, Los Angeles, CA (United States); UCLA
Univ. of California, Los Angeles, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019152

OSTI ID:: 1968773

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 46 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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