Campus Units

Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

2015

Journal or Book Title

Inorganic Chemistry

Volume

54

First Page

922

Last Page

929

DOI

10.1021/ic502326j

Abstract

Zinc clusters are not common for binary intermetallics with relatively low zinc content, but this work shows that zinc clustering can be triggered by lithiation, as exemplified by Ca∼30Li3+xZn60–x, P6/mmm, Z = 1, which can be directly converted from CaZn2. Two end members of the solid solution (x = 0.44 and 1.38) were established and structurally characterized by single-crystal X-ray diffraction analyses: Ca30Li3.44(6)Zn59.56(6), a = 15.4651(9) Å, c = 9.3898(3) Å; Ca30.45(2)Li4.38(6)Zn58.62(6), a = 15.524(3) Å, c = 9.413(2) Å. The structures of Ca∼30Li3+xZn60–xfeature a condensed anionic network of Zn3 triangles, lithium-centered Zn12 icosahedra, and arachno-(Zn,Li)18 tubular clusters that are surrounded respectively by Ca14, Ca20, and Ca30polyhedra. These polyhedra share faces and form a clathrate-like cationic framework. The specific occupation of lithium in the structure is consistent with theoretical “coloring” analyses. Analysis by the linear muffin-tin orbital (LMTO) method within the atomic sphere approximation reveals that Ca∼30Li3+xZn60–x is a metallic, Zintl-like phase with an open-shell electronic structure. The contribution of Ca–Zn polar covalent interactions is about 41%.

Comments

This is an article from Inorganic Chemistry 54 (2015): 922, doi: 10.1021/ic502326j. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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