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Issue 45, 2012
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Synthesis, crystal structure and physical properties of the clathrate-I phase Ba8RhxSi46−xyy

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Abstract

The new clathrate-I phase Ba8RhxSi46−xyy (2.36 < x < 2.74; y = 0.65 for x = 2.74), Pearson symbol cP54, space group Pm[3 with combining macron]n, was prepared as a single phase and characterized. For these compositions, the lattice parameter does not change significantly and was found to be a = 10.347(1) Å. Phase relations were investigated by means of metallographic and thermal analyses. The incongruently melting phase Ba8RhxSi46−xyy was obtained by annealing a solidified melt of the stoichiometric composition at 1000 °C for five days. Below 850 °C, the clathrate phase slowly decomposes to BaSi2, Si and the new compound BaRh2Si9. Crystal structure and vacancy concentration were investigated by means of single crystal and powder X-ray diffraction and wavelength dispersive X-ray spectroscopy analyses. Quantum chemical calculations show that the Rh 4d states hybridize with Si 3p states so that the DOS structure cannot be simply deduced in a rigid band approach from that of the binary Ba8Si46. Analysis of the chemical bonding applying the ELI-D approach yielded covalent two-center two-electron bonds between Rh and Si atoms. For the composition Ba8Rh2.74Si42.610.65, a temperature dependent diamagnetic susceptibility and an almost temperature independent electrical resistivity (ρ ≈ 5 μΩm) were observed. The magnitude of the negative Seebeck coefficient is increasing linearly with temperature from 0 μV K−1 at 2 K to −35 μV K−1 at 850 K indicating n-type electrical conductivity.

Graphical abstract: Synthesis, crystal structure and physical properties of the clathrate-I phase Ba8RhxSi46−x−y□y

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Publication details

The article was received on 02 Jul 2012, accepted on 06 Sep 2012 and first published on 01 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT31432K
Citation: Dalton Trans., 2012,41, 13960-13968
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    Synthesis, crystal structure and physical properties of the clathrate-I phase Ba8RhxSi46−xyy

    W. Jung, H. Kessens, A. Ormeci, W. Schnelle, U. Burkhardt, H. Borrmann, H. D. Nguyen, M. Baitinger and Y. Grin, Dalton Trans., 2012, 41, 13960
    DOI: 10.1039/C2DT31432K

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