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Title: 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 5Au 16(Au/In) 6 structure

The ternary Eu(Au/In) 2 (EuAu 0.46In 1.54 (2)) (I), EuAu 4(Au/In) 2 (EuAu 4+xIn 2–x with x = 0.75(2) (II), 0.93(2), and 1.03(2)), and Eu 5Au 16(Au/In) 6 (Eu 5Au 17.29In 4.71(3)) (III) have been synthesized, and their structures were characterized by single-crystal X-ray diffraction. I and II crystallize with the CeCu 2-type (Pearson Symbol oI12; Imma; Z = 4; a = 4.9018(4) Å; b = 7.8237(5) Å; c = 8.4457(5) Å) and the YbAl 4Mo 2-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 Au 8 prisms enclosing Eu, Au, and In atoms. Combination of these structural motifs leads to a new structure type as observed for Eu 5Au 16(Au/In) 6 (Eu 5Au 17.29In 4.71(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 EuAu 2–“EuAu 4In 2”. The site preferences of the disordered Au/In positions in II were investigated for different hypothetical “EuAu 4(Au/In) 2” models using themore » 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 “EuAu 5In” and “EuAu 4In 2” 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.« less
Authors:
 [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)
Publication Date:
OSTI Identifier:
1239154
Report Number(s):
IS-J-8788
Journal ID: ISSN 0020-1669
Grant/Contract Number:
AC02-07CH11358
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 17; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY