Ba4RuMn2O10: A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers

Callista M. Skaggs; Peter E. Siegfried; Jun Sang Cho; Yan Xin; V. Ovidiu Garlea; Keith M. Taddei; Hari Bhandari; Mark Croft; Nirmal J. Ghimire; Joon I. Jang; Xiaoyan Tan

doi:10.1021/acs.chemmater.4c00586

Ba₄RuMn₂O₁₀: A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers

Callista M. Skaggs, Peter E. Siegfried, Jun Sang Cho, Yan Xin, V. Ovidiu Garlea, Keith M. Taddei, Hari Bhandari, Mark Croft, Nirmal J. Ghimire, Joon I. Jang, Xiaoyan Tan

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Abstract

Phase-pure polycrystalline Ba₄RuMn₂O₁₀ was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc2₁) 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 Ba₄T₃O₁₀ (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. Ba₄RuMn₂O₁₀ is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.(Figure presented.)

Original language	English
Pages (from-to)	6053-6061
Number of pages	9
Journal	Chemistry of Materials
Volume	36
Issue number	12
DOIs	https://doi.org/10.1021/acs.chemmater.4c00586
State	Published - Jun 25 2024

Funding

C.M.S. and X.T. were supported by start-up funding from George Mason University. J.I.J. acknowledges support from the Basic Science Research Programs (2021R1A2C2013625) and Basic Research Laboratory Program (2022R1A4A1033562) through the National Research Foundation of Korea (NRF), funded by the Korean government. N.J.G acknowledges the support from the National Science Foundation (NSF) CAREER award DMR-2143903. TEM work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779, DMR-2128556, and the State of Florida. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory.

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title = "Ba4RuMn2O10: A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers",

abstract = "Phase-pure polycrystalline Ba4RuMn2O10 was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc21) 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 Ba4T3O10 (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. Ba4RuMn2O10 is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.(Figure presented.)",

author = "Skaggs, {Callista M.} and Siegfried, {Peter E.} and Cho, {Jun Sang} and Yan Xin and Garlea, {V. Ovidiu} and Taddei, {Keith M.} and Hari Bhandari and Mark Croft and Ghimire, {Nirmal J.} and Jang, {Joon I.} and Xiaoyan Tan",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society",

year = "2024",

month = jun,

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doi = "10.1021/acs.chemmater.4c00586",

language = "English",

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AU - Skaggs, Callista M.

AU - Siegfried, Peter E.

AU - Cho, Jun Sang

AU - Xin, Yan

AU - Garlea, V. Ovidiu

AU - Taddei, Keith M.

AU - Bhandari, Hari

AU - Croft, Mark

AU - Ghimire, Nirmal J.

AU - Jang, Joon I.

AU - Tan, Xiaoyan

PY - 2024/6/25

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N2 - Phase-pure polycrystalline Ba4RuMn2O10 was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc21) 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 Ba4T3O10 (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. Ba4RuMn2O10 is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.(Figure presented.)

AB - Phase-pure polycrystalline Ba4RuMn2O10 was prepared and determined to adopt the noncentrosymmetric polar crystal structure (space group Cmc21) 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 Ba4T3O10 (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. Ba4RuMn2O10 is a narrow bandgap (∼0.6 eV) semiconductor exhibiting spin-glass behavior with strong magnetic frustration and antiferromagnetic interactions.(Figure presented.)

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Ba₄RuMn₂O₁₀: A Noncentrosymmetric Polar Crystal Structure with Disordered Trimers

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