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Title: From the ternary Eu(Au/In)2 and EuAu4(Au/In)2 with remarkable Au/In distributions to a new structure type: The gold-rich Eu5Au16(Au/In)6 structure

Journal Article · · Inorganic Chemistry
 [1];  [2];  [1]
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
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The ternary Eu(Au/In)2 (EuAu0.46In1.54(2)) (I), EuAu4(Au/In)2 (EuAu4+xIn2–x with x = 0.75(2) (II), 0.93(2), and 1.03(2)), and Eu5Au16(Au/In)6 (Eu5Au17.29In4.71(3)) (III) have been synthesized, and their structures were characterized by single-crystal X-ray diffraction. I and II crystallize with the CeCu2-type (Pearson Symbol oI12; Imma; Z = 4; a = 4.9018(4) Å; b = 7.8237(5) Å; c = 8.4457(5) Å) and the YbAl4Mo2-type (tI14; I4/mmm; Z = 2; a = 7.1612(7) Å; c = 5.5268(7) Å) and exhibit significant Au/In disorder. I is composed of an Au/In-mixed diamond-related host lattice encapsulating Eu atoms, while the structure of II features ribbons of distorted, squared Au8 prisms enclosing Eu, Au, and In atoms. Combination of these structural motifs leads to a new structure type as observed for Eu5Au16(Au/In)6 (Eu5Au17.29In4.71(3)) (oS108; Cmcm; Z = 4; a = 7.2283(4) Å; b = 9.0499(6) Å; c = 34.619(2) Å), which formally represents a one-dimensional intergrowth of the series EuAu2–“EuAu4In2”. The site preferences of the disordered Au/In positions in II were investigated for different hypothetical “EuAu4(Au/In)2” models using the projector-augmented wave method and indicate that these structures attempt to optimize the frequencies of the heteroatomic Au–In contacts. Furthermore, a chemical bonding analysis on two “EuAu5In” and “EuAu4In2” models employed the TB-LMTO-ASA method and reveals that the subtle interplay between the local atomic environments and the bond energies determines the structural and site preferences for these systems.

Research Organization:
Ames Lab., Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1239154
Report Number(s):
IS-J-8788
Journal Information:
Inorganic Chemistry, Vol. 54, Issue 17; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

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Cited By (9)

Revealing Tendencies in the Electronic Structures of Polar Intermetallic Compounds journal February 2018
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride journal May 2019
Squares of gold atoms and linear infinite chains of Cd atoms as building units in the intermetallic phases REAu4Cd2 (RE=La–Nd, Sm) with YbAl4Mo2-type structure journal February 2020
Antiferromagnetic semiconductor Eu 3 Sn 2 P 4 with Sn–Sn dimer and crown-wrapped Eu journal January 2019
The Crystal Orbital Hamilton Population (COHP) Method as a Tool to Visualize and Analyze Chemical Bonding in Intermetallic Compounds text January 2018
Revealing the Nature of Bonding in Rare-Earth Transition-Metal Tellurides by Means of Methods Based on First Principles: Revealing the Nature of Bonding in Rare-Earth Transition-Metal Tellurides by Means of Methods Based on First Principles journal July 2017
Revealing Tendencies in the Electronic Structures of Polar Intermetallic Compounds text January 2018
Revealing the Nature of Chemical Bonding in an ALn2Ag3Te5-Type Alkaline-Metal (A) Lanthanide (Ln) Silver Telluride text January 2019
The Crystal Orbital Hamilton Population (COHP) Method as a Tool to Visualize and Analyze Chemical Bonding in Intermetallic Compounds journal May 2018

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