Ba(4)RuMn(2)O(10): A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers

Ba(4)RuMn(2)O(10):具有无序三聚体的非中心对称极性晶体结构

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Abstract

Phase-pure polycrystalline Ba(4)RuMn(2)O(10) was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc2(1)) based on results of second harmonic generation, convergent beam electron diffraction, and Rietveld refinements using powder neutron diffraction data. The crystal structure features zigzag chains of corner-shared trimers, which contain three distorted face-sharing octahedra. The three metal sites in the trimers are occupied by disordered Ru/Mn with three different ratios: Ru1:Mn1 = 0.202(8):0.798(8), Ru2:Mn2 = 0.27(1):0.73(1), and Ru3:Mn3 = 0.40(1):0.60(1), successfully lowering the symmetry and inducing the polar crystal structure from the centrosymmetric parent compounds Ba(4)T(3)O(10) (T = Mn, Ru; space group Cmca). The valence state of Ru/Mn is confirmed to be +4 according to X-ray absorption near-edge spectroscopy. Ba(4)RuMn(2)O(10) is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.

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