Campus Units

Ames Laboratory, Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2012

Journal or Book Title

Inorganic Chemistry

Volume

51

Issue

16

First Page

8882

Last Page

8889

DOI

10.1021/ic300866q

Abstract

Bergman-type phases in the Na–Au–T (T = Ga, Ge, and Sn) systems were synthesized by solid-state means and structurally characterized by single-crystal X-ray diffraction studies. Two structurally related (1/1) Bergman phases were found in the Na–Au–Ga system: (a) a conventional Bergman-type (CB) structure, Na26AuxGa54–x, which features empty innermost icosahedra, as refined with x = 18.1 (3), Im3̅, a = 14.512(2) Å, and Z = 2; (b) a stuffed Bergman-type (SB) structure, Na26AuyGa55–y, which contains Ga-centered innermost icosahedra, as refined with y = 36.0 (1), Im3̅, a = 14.597(2) Å, and Z = 2. Although these two subtypes have considerable phase widths along with respective tie lines at Na ≈ 32.5 and 32.1 atom %, they do not merge into a continuous solid solution. Rather, a quasicrystalline phase close to the Au-poor CB phase and an orthorhombic derivative near the Au-rich SB phase lie between them. In contrast, only Au-rich SB phases exist in the Ge and Sn systems, in which the innermost icosahedra are centered by Au rather than Ge or Sn. These were refined for Na26Au40.93(5)Ge14.07(5) (Im3̅, a = 14.581(2) Å, and Z = 2) and Na26Au39.83(6)Sn15.17(6) (Im3̅, a = 15.009(2) Å, and Z = 2), respectively. Occupations of the centers of Bergman clusters are rare. Such centering and coloring correlate with the sizes of the neighboring icosahedra, the size ratios between electropositive and electronegative components, and the values of the average valence electron count per atom (e/a). Theoretical calculations revealed that all of these phases are Hume–Rothery phases, with evident pseudogaps in the density of states curves that arise from the interactions between Fermi surface and Brillouin zone boundaries corresponding to a strong diffraction intensity.

Comments

Reprinted (adapted) with permission from Inorg. Chem., 2012, 51 (16), pp 8882–8889. Copyright 2012 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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