Lithiation-Induced Zinc Clustering of Zn3, Zn12, and Zn18 Units in Zintl-Like Ca∼ 30Li3+ xZn60–x (x= 0.44–1.38)
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Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.
For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.
The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).
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The Department of Chemistry was founded in 1880.
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1880-present
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- College of Liberal Arts and Sciences (parent college)
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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%.
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This is an article from Inorganic Chemistry 54 (2015): 922, doi: 10.1021/ic502326j. Posted with permission.