4.7 Article

Valence fluctuations in the 3D+3 modulated Yb3Co4Ge13 Remeika phase

Journal

DALTON TRANSACTIONS
Volume 50, Issue 38, Pages 13580-13590

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1dt01972d

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Funding

  1. Deutsche Forschungsgemeinschaft (DFG) [325295543]

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Yb3Co4Ge13 is the first example of a Remeika phase with a unique crystal structure. Slight adjustments in its chemical composition lead to changes in the crystal structure, with Yb ions exhibiting different intermediate valence states at different temperatures.
Yb3Co4Ge13 is the first example of a Remeika phase with a 3D + 3 [space group P43n(alpha,0,0)000(0,alpha,0)000(0,0,alpha)000; a = 8.72328(1) angstrom, alpha = 0.4974(2)] modulated crystal structure. A slight shift of the composition towards higher Yb-content (i.e. Yb3.2Co4Ge12.8) leads to the disappearance of the satellite reflections and stabilization of the disordered primitive cubic [space group Pm3n, a = 8.74072(2) angstrom] Remeika prototype structure. The stoichiometric structurally modulated germanide is a metal with hole-like charge carriers, where Yb-ions are in a temperature-dependent intermediate valence state varying from +2.60 to +2.66 for the temperature range 85-293 K. The valence fluctuations have been investigated by means of temperature dependent X-ray absorption spectroscopy, magnetic susceptibility and thermopower measurements.

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