Crystal and electronic structure of the ternary Zintl bismuthide BaLiBi
Date
2023-10-02
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Zeitschrift für anorganische und allgemeine Chemie | Journal of Inorganic and General Chemistry
Abstract
Reported is the accurate refinement of the structure of the ternary bismuthide BaLiBi, based on single-crystal X-ray diffraction data. This compound crystallizes with the ZrBeSi structure type with the space group P63/mmc (no. 194), a=4.9917(6) Å, c=9.079(2) Å, V=195.92(7) Å3 with two formula units per unit cell. In addition to being a colored ternary variant of the AlB2 type, the crystal structure of BaLiBi can be also viewed as a “stuffed” variant of the NiAs structure, where the Bi atoms form a hexagonal close packing, the Ba atoms occupy the octahedral voids in this packing, and the Li atoms are located between adjacent tetrahedral voids on their common triangular faces. In the absence of direct Bi–Bi interactions, the BaLiBi crystal structure rationalized according to the notation (Ba2+)(Li+)(Bi3−), suggesting an electron-balanced composition, i. e., a Zintl phase. In line with this notation, scalar-relativistic first-principle calculations with the LMTO code reveal a semiconducting ground state, with a bandgap of about 0.6 eV. Fully relativistic electronic structure calculations predict a semimetallic ground state.
Description
This is the peer reviewed version of the following article: Ovchinnikov, Alexander, and Svilen Bobev. “Crystal and Electronic Structure of the Ternary Zintl Bismuthide BaLiBi.” Zeitschrift Für Anorganische Und Allgemeine Chemie 649, no. 19 (October 2, 2023): e202300128. https://doi.org/10.1002/zaac.202300128, which has been published in final form at https://doi.org/10.1002/zaac.202300128. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.. © 2023 Wiley-VCH GmbH. Dedicated to Professor Michael Ruck on the Occasion of His 60th Birthday. This article will be embargoed until 10/02/2024.
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Citation
Ovchinnikov, Alexander, and Svilen Bobev. “Crystal and Electronic Structure of the Ternary Zintl Bismuthide BaLiBi.” Zeitschrift Für Anorganische Und Allgemeine Chemie 649, no. 19 (October 2, 2023): e202300128. https://doi.org/10.1002/zaac.202300128.