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説明:

Large lattice responses in dense inorganic oxides are typically driven by structural phase transitions or redox processes that alter crystal symmetry or composition. Here, we identify a distinct mechanism for such responses: giant lattice expansion through symmetry-preserving cation redistribution in a metastable, structurally frustrated dense oxide. High-pressure-quenched Ba4Ru3O12 undergoes an irreversible volumetric expansion of 4.4% between 450 and 650 K while retaining R-3m symmetry and oxygen stoichiometry. High-resolution synchrotron diffraction reveals cooperative redistribution of Ru within face-sharing RuO6 trimers, directly linking intratrimer cation configuration to lattice volume. Thermogravimetric, transport, and magnetic measurements exclude decomposition, redox processes, and electronic or magnetic phase transitions. First-principles calculations show that compression stabilizes a low-volume cation configuration, which is retained after recovery to ambient pressure and relaxes upon heating through intratrimer cation exchange. Together, these results establish symmetry-preserving cation redistribution as a mechanism for giant lattice responses in dense oxides and identify metastable frustrated configurations as a route to large structural responses without symmetry breaking or compositional change.

権利情報:

• Creative Commons BY Attribution 4.0 International
  

キーワード: High-pressure synthesis, Irreversible expansion, Barium ruthenate, Atomic rearrangement, Thermal stress control

刊行年月日: 2026-06-03

出版者: American Chemical Society (ACS)

掲載誌:

• Journal of the American Chemical Society (ISSN: 00027863) vol. 148 issue. 21 p. 22380-22388

研究助成金:

• National Institute for Materials Science (NIMS)
• JSPS KAKENHI JP25K01507
• JSPS KAKENHI JP25K01657
• World Premier International Research Center Initiative (WPI), MEXT, Japan

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1021/jacs.6c07579

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更新時刻: 2026-06-04 15:54:31 +0900

MDRでの公開時刻: 2026-06-04 18:32:33 +0900