Abstract
BaSi3 is obtained at pressures between 12(2) and 15(2) GPa and temperatures from 800(80) and 1050(105) K applied for one to five hours before quenching. The new trisilicide crystallizes in the space group I2m (no. 121) and adopts a unique atomic arrangement which is a distorted variant of the CaGe3 type. At ambient pressure and 570(5) K, the compound decomposes in an exothermal reaction into (hP3)BaSi2 and two amorphous silicon-rich phases. Chemical bonding analysis reveals covalent bonding in the silicon partial structure and polar multicenter interactions between the silicon layers and the barium atoms. The temperature dependence of electrical resistivity and magnetic susceptibility measurements indicate metallic behavior.
Highlights
The Zintl-Klemm concept [1,2] constitutes a powerful framework for understanding the interdependence of chemical bonding and electron count of a rich variety of binary phases formed by element semiconductors such as silicon or germanium with electropositive partners of the alkaline, alkaline earth- and rare-earth metal groups
We describe high-pressure high-temperature synthesis, crystal structure and chemical bonding properties of BaSi3 as well as the temperature dependence of electrical resistivity and magnetic susceptibility
Barium trisilicide was prepared by high-pressure high-temperature synthesis
Summary
The Zintl-Klemm concept [1,2] constitutes a powerful framework for understanding the interdependence of chemical bonding and electron count of a rich variety of binary phases formed by element semiconductors such as silicon or germanium with electropositive partners of the alkaline-, alkaline earth- and rare-earth metal groups. A systematic study of tetrel connectivities in polyanions revealed a variety of motifs with composition MT3 (M = Ca, Sr, Ba, Y, La, Ce, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu; T = Si, Ge) [8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27] All of these exceed the scope of the 8-N rule and show interesting physical properties such as superconductivity. We describe high-pressure high-temperature synthesis, crystal structure and chemical bonding properties of BaSi3 as well as the temperature dependence of electrical resistivity and magnetic susceptibility
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