Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6

Smetana, Volodymyr; Steinberg, Simon; Mudring, Anja-Verena

doi:10.1021/acs.cgd.6b01536

Title: Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu _1.4 Ga _2.8 and CsAu ₂ Ga _2.6

Journal Article · Tue Dec 27 00:00:00 EST 2016 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.6b01536· OSTI ID:1347910

Smetana, Volodymyr ^[1]; Steinberg, Simon ^[1];

^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Material Sciences and Engineering

Gold intermetallics are known for their unusual structures and bonding patterns. Two new compounds have been discovered in the cation-poor part of the Cs–Au–Ga system. We obtained both compounds directly by heating the elements at elevated temperatures. Structure determinations based on single-crystal X-ray diffraction analyses revealed two structurally and compositionally related formations: CsAu_1.4Ga_2.8 (I) and CsAu₂Ga_2.6 (II) crystallize in their own structure types (I: R$$\bar{3}$$, a = 11.160(2) Å, c = 21.706(4) Å, Z = 18; II: R$$\bar{3}$$, a = 11.106(1) Å, Å, c = 77.243(9) Å, Z = 54) and contain hexagonal cationic layers of cesium. Furthermore, this is a unique structural motif, which has never been observed for the other (lighter) alkali metals in combination with Au and post transition elements. The polyanionic part is characterized in contrast by Au/Ga tetrahedral stars, a structural feature that is characteristic for light alkali metal representatives, and disordered sites with mixed Au/Ga occupancies that occur in both structures with a more significant disorder in the polyanionic component of CsAu₂Ga_2.6. Examinations of the electronic band structure for a model approximating the composition of CsAu_1.4Ga_2.8 have been completed using density-functional-theory-based methods and reveal a deep pseudogap at E_F. Bonding analysis by evaluating the crystal orbital Hamilton populations show dominant heteroatomic Au–Ga bonds and only a negligible contribution from Cs pairs.

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Research Organization:: Ames Lab., Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1347910

Report Number(s):: IS-J 9238

Journal Information:: Crystal Growth and Design, Vol. 17, Issue 2; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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Title: Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6

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Title: Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu _1.4 Ga _2.8 and CsAu ₂ Ga _2.6