Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6
Abstract
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: CsAu1.4Ga2.8 (I) and CsAu2Ga2.6 (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 CsAu2Ga2.6. Examinations of the electronic band structure for a model approximating the composition of CsAu1.4Ga2.8 have been completed using density-functional-theory-based methods and reveal a deep pseudogap at EF. Bonding analysis by evaluating the crystal orbital Hamilton populations show dominant heteroatomic Au–Ga bonds and only a negligible contribution from Cs pairs.
- Authors:
-
- Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Material Sciences and Engineering
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1347910
- Report Number(s):
- IS-J 9238
Journal ID: ISSN 1528-7483
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Crystal Growth and Design
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 2; Journal ID: ISSN 1528-7483
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Smetana, Volodymyr, Steinberg, Simon, and Mudring, Anja-Verena. Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6. United States: N. p., 2016.
Web. doi:10.1021/acs.cgd.6b01536.
Smetana, Volodymyr, Steinberg, Simon, & Mudring, Anja-Verena. Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6. United States. https://doi.org/10.1021/acs.cgd.6b01536
Smetana, Volodymyr, Steinberg, Simon, and Mudring, Anja-Verena. Tue .
"Layered Structures and Disordered Polyanionic Nets in the Cation-Poor Polar Intermetallics CsAu 1.4 Ga 2.8 and CsAu 2 Ga 2.6". United States. https://doi.org/10.1021/acs.cgd.6b01536. https://www.osti.gov/servlets/purl/1347910.
@article{osti_1347910,
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},
author = {Smetana, Volodymyr and Steinberg, Simon and Mudring, Anja-Verena},
abstractNote = {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: CsAu1.4Ga2.8 (I) and CsAu2Ga2.6 (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 CsAu2Ga2.6. Examinations of the electronic band structure for a model approximating the composition of CsAu1.4Ga2.8 have been completed using density-functional-theory-based methods and reveal a deep pseudogap at EF. Bonding analysis by evaluating the crystal orbital Hamilton populations show dominant heteroatomic Au–Ga bonds and only a negligible contribution from Cs pairs.},
doi = {10.1021/acs.cgd.6b01536},
journal = {Crystal Growth and Design},
number = 2,
volume = 17,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2016},
month = {Tue Dec 27 00:00:00 EST 2016}
}
Web of Science
Works referenced in this record:
The Structure of the Diamond
journal, September 1913
- Bragg, W. H.; Bragg, W. L.
- Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 89, Issue 610
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
Minimal basis sets in the linear muffin-tin orbital method: Application to the diamond-structure crystals C, Si, and Ge
journal, August 1986
- Lambrecht, Walter R. L.; Andersen, O. K.
- Physical Review B, Vol. 34, Issue 4
Cation-Poor Complex Metallic Alloys in Ba(Eu)–Au–Al(Ga) Systems: Identifying the Keys that Control Structural Arrangements and Atom Distributions at the Atomic Level
journal, October 2015
- Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav
- Inorganic Chemistry, Vol. 54, Issue 21
Das Verhalten der Alkalimetalle zu Kupfer, Silber und Gold
journal, June 1961
- Kienast, Gerhard; Verma, Jitendra; Klemm, Wilhelm
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 310, Issue 3
Three Alkali-Metal–Gold–Gallium Systems. Ternary Tunnel Structures and Some Problems with Poorly Ordered Cations
journal, April 2012
- Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.
- Inorganic Chemistry, Vol. 51, Issue 14
An empirical correction for absorption anisotropy
journal, January 1995
- Blessing, R. H.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 51, Issue 1
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
New real ternary and pseudoternary phases in the Li–Au–In system
journal, May 2011
- Dmytriv, G. S.; Pavlyuk, V. V.; Pauly, H.
- Journal of Solid State Chemistry, Vol. 184, Issue 5
K4Au8Ga: eine Auffüllungsvariante des MgCu2-Typs
journal, September 2000
- Müller, Jürgen; Zachwieja, Uwe
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 626, Issue 9
Na2Au6In5, the first compound in the system sodium-gold-indium
journal, March 1996
- Zachwieja, Uwe
- Journal of Alloys and Compounds, Vol. 235, Issue 1
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Na8Au9.8(4)Ga7.2 and Na17Au5.87(2)Ga46.63: The diversity of pseudo 5-fold symmetries in the Na–Au–Ga system
journal, November 2013
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Journal of Solid State Chemistry, Vol. 207
Explicit, First-Principles Tight-Binding Theory
journal, December 1984
- Andersen, O. K.; Jepsen, O.
- Physical Review Letters, Vol. 53, Issue 27
Participation of Sodium in the Bonding of Anionic Networks: Synthesis, Structure, and Bonding of Na 3 MIn 2 (M = Au, Ag)
journal, September 2005
- Li, Bin; Corbett, John D.
- Inorganic Chemistry, Vol. 44, Issue 19
Late transition metal anions acting as p-metal elements
journal, April 2008
- Köhler, Jürgen; Whangbo, Myung-Hwan
- Solid State Sciences, Vol. 10, Issue 4
Absolute electronegativity and hardness: application to inorganic chemistry
journal, February 1988
- Pearson, Ralph G.
- Inorganic Chemistry, Vol. 27, Issue 4
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
From the Ternary Eu(Au/In) 2 and EuAu 4 (Au/In) 2 with Remarkable Au/In Distributions to a New Structure Type: The Gold-Rich Eu 5 Au 16 (Au/In) 6 Structure
journal, August 2015
- Steinberg, Simon; Card, Nathan; Mudring, Anja-Verena
- Inorganic Chemistry, Vol. 54, Issue 17
Electrical and thermal transport properties of icosahedral and decagonal quasicrystals
journal, January 2012
- Dolinšek, Janez
- Chemical Society Reviews, Vol. 41, Issue 20
Relativity and the periodic system of elements
journal, August 1979
- Pyykko, Pekka; Desclaux, Jean Paul
- Accounts of Chemical Research, Vol. 12, Issue 8
Conventional and Stuffed Bergman-Type Phases in the Na–Au–T (T = Ga, Ge, Sn) Systems: Syntheses, Structures, Coloring of Cluster Centers, and Fermi Sphere–Brillouin Zone Interactions
journal, August 2012
- Lin, Qisheng; Smetana, Volodymyr; Miller, Gordon J.
- Inorganic Chemistry, Vol. 51, Issue 16
Intermetallic Compounds with 1D Infinite Tunnels. Syntheses and Structures of AAu 4 In 2 (A = K, Rb)
journal, September 2006
- Li, Bin; Corbett, John D.
- Journal of the American Chemical Society, Vol. 128, Issue 38
Electronic Stabilization Effects: Three New K−In−T (T = Mg, Au, Zn) Network Compounds
journal, October 2006
- Li, Bin; Corbett, John D.
- Inorganic Chemistry, Vol. 45, Issue 22
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Different Cation Arrangements in Au−In Networks. Syntheses and Structures of Six Intermetallic Compounds in Alkali-Metal−Au−In Systems
journal, July 2007
- Li, Bin; Corbett, John D.
- Inorganic Chemistry, Vol. 46, Issue 15
Gold Tetrahedra as Building Blocks in K 3 Au 5 Tr (Tr = In, Tl) and Rb 2 Au 3 Tl and in Other Compounds: A Broad Group of Electron-Poor Intermetallic Phases
journal, July 2009
- Li, Bin; Kim, Sung-Jin; Miller, Gordon J.
- Inorganic Chemistry, Vol. 48, Issue 14
Bonding Patterns in Intermetallic Compounds
journal, July 1991
- Nesper, Reinhard
- Angewandte Chemie International Edition in English, Vol. 30, Issue 7
Intermetallic NaAu 2 as a Heterogeneous Catalyst for Low-Temperature CO Oxidation
journal, June 2013
- Xiao, Chaoxian; Wang, Lin-Lin; Maligal-Ganesh, Raghu V.
- Journal of the American Chemical Society, Vol. 135, Issue 26
Crystal structure of potassium indium (22 – x/39+x) (x = 0.67), K 21.33 In 39.67
journal, January 1992
- Cordier, G.; Müller, V.
- Zeitschrift für Kristallographie, Vol. 198, Issue 3-4
Synthesis and Crystal Structure of the New Quaternary Subnitride Na15Li8Ba12N6
journal, October 2007
- Smetana, Volodymyr; Babizhetskyy, Volodymyr; Vajenine, Grigori V.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 633, Issue 13-14
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
NaAuIn2, ein tern�res Aurid mit ethananalogen In2Au6-Baueinheiten und?1[In2/2]-Ketten
journal, October 1995
- Zachwieja, Uwe
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 621, Issue 10
A Sodium-Containing Quasicrystal: Using Gold To Enhance Sodium’s Covalency in Intermetallic Compounds
journal, November 2012
- Smetana, Volodymyr; Lin, Qisheng; Pratt, Daniel K.
- Angewandte Chemie International Edition, Vol. 51, Issue 51
Four Polyanionic Compounds in the K–Au–Ga System: A Case Study in Exploratory Synthesis and of the Art of Structural Analysis
journal, January 2012
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Inorganic Chemistry, Vol. 51, Issue 3
Relativistic effects in structural chemistry
journal, May 1988
- Pyykko, Pekka
- Chemical Reviews, Vol. 88, Issue 3
Na4AuTl, die erste tern�re Verbindung im System Natrium/Gold/Thallium
journal, October 1997
- Zachwieja, Uwe; M�ller, J�rgen
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 623, Issue 10
Theoretical Chemistry of Gold
journal, August 2004
- Pyykkö, Pekka
- Angewandte Chemie International Edition, Vol. 43, Issue 34
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
Novel oxidation of RbGa3 through substitution of gold for gallium—a reapportionment of the dodecahedral clusters
journal, May 2002
- Henning, Robert W.; Corbett, John D.
- Journal of Alloys and Compounds, Vol. 338, Issue 1-2
Complex Polyanionic Nets in RbAu 4.01(2) Ga 8.64(5) and CsAu 5 Ga 9 : The Role of Cations in the Formation of New Polar Intermetallics : Complex Polyanionic Nets in RbAu
journal, February 2014
- Smetana, Volodymyr; Corbett, John D.; Miller, Gordon J.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 640, Issue 5
Syntheses optimization, structural and thermoelectric properties of 1/1 Tsai-type quasicrystal approximants in RE–Au–SM systems (RE=Yb, Gd and SM=Si, Ge)
journal, March 2013
- Gebresenbut, Girma Hailu; Tamura, Ryuji; Eklöf, Daniel
- Journal of Physics: Condensed Matter, Vol. 25, Issue 13
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
Polyclusters and Substitution Effects in the Na–Au–Ga System: Remarkable Sodium Bonding Characteristics in Polar Intermetallics
journal, October 2013
- Smetana, Volodymyr; Miller, Gordon J.; Corbett, John D.
- Inorganic Chemistry, Vol. 52, Issue 21
The Hume–Rothery electron concentration rule for a series of gamma-brasses studied by full-potential linearized augmented plane wave (FLAPW)
journal, January 2006
- Mizutani, U.; Asahi, R.; Sato, H.
- Philosophical Magazine, Vol. 86, Issue 3-5
Na8Au11In6: ein Gold - Indium-Polyederger�st mit pentagonal-bipyramidalen AuAu5In-Baueinheiten
journal, September 1996
- Zachwieja, Uwe
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 9
Crystal structure of sodium gold gallium, Na 128 Au 81 Ga 275
journal, February 1993
- ,
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 206, Issue 2
Works referencing / citing this record:
Revisiting the Zintl‒Klemm Concept for ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Tellurides
journal, March 2020
- Eickmeier, Katharina; Fries, Kai; Gladisch, Fabian
- Crystals, Vol. 10, Issue 3
Revisiting the Zintl‒Klemm Concept for ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Tellurides
text, January 2020
- Eickmeier, Katharina; Fries, Kai S.; Gladisch, Fabian C.
- RWTH Aachen University
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride
journal, May 2019
- Göbgen, Kai C.; Fries, Kai S.; Gladisch, Fabian C.
- Inorganics, Vol. 7, Issue 6
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride
text, January 2019
- Göbgen, Kai C.; Fries, Kai S.; Gladisch, Fabian C.
- RWTH Aachen University