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Title: Universal geometric frustration in pyrochlores

Abstract

Materials with the pyrochlore/fluorite structure have diverse technological applications, from magnetism to nuclear waste disposal. Here we report the observation of structural instability present in the pyrochlores A 2Zr 2O 6O' (A = Pr, La) and Yb 2Ti 2O 6O', that exists despite ideal stoichiometry, ideal cation-ordering, the absence of lone pair effects, and a lack of magnetic order. Though these materials appear to have good long-range order, local structure probes find displacements, of the order of 0.01 nm, within the pyrochlore framework. The pattern of displacements of the A 2O' sublattice mimics the entropically-driven fluxional motions characteristic of and well-known in the silica mineral β-cristobalite. The universality of such displacements within the pyrochlore structure adds to the known structural diversity and explains the extreme sensitivity to composition found in quantum spin ices and the lack of ferroelectric behavior in pyrochlores.

Authors:
 [1];  [2];  [2];  [2];  [2];  [3];  [4];  [5];  [6];  [6];  [7]; ORCiD logo [6];  [2];  [2]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Johns Hopkins Univ., Baltimore, MD (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
  3. STFC Daresbury Campus, Daresbury (United Kingdom)
  4. Univ. of Leeds (United Kingdom)
  5. Forschungszentrum Jülich GmbH (Germany)
  6. Univ. of Tokyo, Kashiwa, Chiba (Japan)
  7. Osaka Univ. (Japan)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1459972
Grant/Contract Number:  
FG02-08ER46544; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Trump, B. A., Koohpayeh, S. M., Livi, K. J. T., Wen, J. -J., Arpino, K. E., Ramasse, Q. M., Brydson, R., Feygenson, M., Takeda, H., Takigawa, M., Kimura, K., Nakatsuji, S., Broholm, C. L., and McQueen, T. M. Universal geometric frustration in pyrochlores. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05033-7.
Trump, B. A., Koohpayeh, S. M., Livi, K. J. T., Wen, J. -J., Arpino, K. E., Ramasse, Q. M., Brydson, R., Feygenson, M., Takeda, H., Takigawa, M., Kimura, K., Nakatsuji, S., Broholm, C. L., & McQueen, T. M. Universal geometric frustration in pyrochlores. United States. doi:10.1038/s41467-018-05033-7.
Trump, B. A., Koohpayeh, S. M., Livi, K. J. T., Wen, J. -J., Arpino, K. E., Ramasse, Q. M., Brydson, R., Feygenson, M., Takeda, H., Takigawa, M., Kimura, K., Nakatsuji, S., Broholm, C. L., and McQueen, T. M. Thu . "Universal geometric frustration in pyrochlores". United States. doi:10.1038/s41467-018-05033-7. https://www.osti.gov/servlets/purl/1459972.
@article{osti_1459972,
title = {Universal geometric frustration in pyrochlores},
author = {Trump, B. A. and Koohpayeh, S. M. and Livi, K. J. T. and Wen, J. -J. and Arpino, K. E. and Ramasse, Q. M. and Brydson, R. and Feygenson, M. and Takeda, H. and Takigawa, M. and Kimura, K. and Nakatsuji, S. and Broholm, C. L. and McQueen, T. M.},
abstractNote = {Materials with the pyrochlore/fluorite structure have diverse technological applications, from magnetism to nuclear waste disposal. Here we report the observation of structural instability present in the pyrochlores A2Zr2O6O' (A = Pr, La) and Yb2Ti2O6O', that exists despite ideal stoichiometry, ideal cation-ordering, the absence of lone pair effects, and a lack of magnetic order. Though these materials appear to have good long-range order, local structure probes find displacements, of the order of 0.01 nm, within the pyrochlore framework. The pattern of displacements of the A2O' sublattice mimics the entropically-driven fluxional motions characteristic of and well-known in the silica mineral β-cristobalite. The universality of such displacements within the pyrochlore structure adds to the known structural diversity and explains the extreme sensitivity to composition found in quantum spin ices and the lack of ferroelectric behavior in pyrochlores.},
doi = {10.1038/s41467-018-05033-7},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

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    Works referencing / citing this record:

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    journal, March 1995

    • Kunz, Martin; Brown, I. David
    • Journal of Solid State Chemistry, Vol. 115, Issue 2
    • DOI: 10.1006/jssc.1995.1150

    Structured Diffuse Scattering as an Indicator of Inherent Cristobalite-like Displacive Flexibility in the Rare Earth Zirconate Pyrochlore LaδZr1−δO2−δ/2, 0.49<δ<0.51
    journal, February 1999

    • Tabira, Yasunori; Withers, Ray; Thompson, John
    • Journal of Solid State Chemistry, Vol. 142, Issue 2
    • DOI: 10.1006/jssc.1998.8054

    Systematic Structural Change in Selected Rare Earth Oxide Pyrochlores as Determined by Wide-Angle CBED and a Comparison with the Results of Atomistic Computer Simulation
    journal, August 2000

    • Tabira, Yasunori; Withers, Ray L.; Minervini, Licia
    • Journal of Solid State Chemistry, Vol. 153, Issue 1
    • DOI: 10.1006/jssc.2000.8712

    The Strain-Driven Pyrochlore to “Defect Fluorite” Phase Transition in Rare Earth Sesquioxide Stabilized Cubic Zirconias
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    • Tabira, Y.; Withers, R. L.; Barry, J. C.
    • Journal of Solid State Chemistry, Vol. 159, Issue 1
    • DOI: 10.1006/jssc.2001.9139

    Systematics of the pyrochlore structure type, ideal A2B2X6Y
    journal, June 1984


    Oxide pyrochlores — A review
    journal, January 1983

    • Subramanian, M. A.; Aravamudan, G.; Subba Rao, G. V.
    • Progress in Solid State Chemistry, Vol. 15, Issue 2
    • DOI: 10.1016/0079-6786(83)90001-8

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    • Esquivel-Elizondo, J. Roberto; Hinojosa, Beverly Brooks; Nino, Juan C.
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    Two-dimensional detector software: From real detector to idealised image or two-theta scan
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    Real-space refinement of single-crystal electron diffuse scattering and its application to Bi 2 Ru 2 O 7−δ
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    PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
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    Frustrated ferroelectricity in niobate pyrochlores
    journal, April 2008


    Reverse Monte Carlo neutron scattering study of the ‘ordered-ice’ oxide pyrochlore Pb 2 Ru 2 O 6.5
    journal, July 2011


    Pyrochlore Structural Chemistry: Predicting the Lattice Constant by the Ionic Radii and Electronegativities of the Constituting Ions
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    Smart Align—a new tool for robust non-rigid registration of scanning microscope data
    journal, July 2015

    • Jones, Lewys; Yang, Hao; Pennycook, Timothy J.
    • Advanced Structural and Chemical Imaging, Vol. 1, Issue 1
    • DOI: 10.1186/s40679-015-0008-4

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