Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study

Kalland, Liv-Elisif; Magrasó, Anna; Mancini, Alessandro; Tealdi, Cristina; Malavasi, Lorenzo

doi:10.1021/cm401466r

Title: Local Structure of Proton-Conducting Lanthanum Tungstate La_28-xW_4+xO_54+δ: a Combined Density Functional Theory and Pair Distribution Function Study

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Abstract

Lanthanum tungstate (La_28–xW_4+xO_54+δ) is a good proton conductor and exhibits a complex fluorite-type structure. To gain further understanding of the short-range order in the structure we correlate the optimized configurations obtained by density functional theory (DFT) with the experimental atomic pair distribution function analysis (PDF) of time-of-flight neutron and synchrotron X-ray data, collected at room temperature. The local atomic arrangements cannot be described by means of any average symmetric structure. Tungsten forms WO₆ octahedra in alternating directions, La1 is mainly 8-fold coordinated in relatively symmetric cubes, and La2 is coordinated with 6 or 7 oxygens in heavily distorted cubes. Both DFT and PDF confirm that the excess tungsten (x) is incorporated in La2 (1/4, 1/4, 1/4) sites in the La₂₇W₅O_55.5 composition. This additional tungsten can be considered as a donor self-dopant in the material and has implications to the conducting properties and the defect structure.

Authors:

Kalland, Liv-Elisif; Magrasó, Anna; Mancini, Alessandro; Tealdi, Cristina; Malavasi, Lorenzo ^[1]

Oslo

Publication Date:: Wed Oct 02 00:00:00 EDT 2013

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: FOREIGN

OSTI Identifier:: 1088573

Resource Type:: Journal Article

Journal Name:: Chemistry of Materials

Additional Journal Information:: Journal Volume: 25; Journal Issue: (11) ; 06, 2013; Journal ID: ISSN 0897-4756

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: ENGLISH

Citation Formats


                    Kalland, Liv-Elisif, Magrasó, Anna, Mancini, Alessandro, Tealdi, Cristina, Malavasi, Lorenzo, and Pavia). Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study.  United States: N. p., 2013. 
        Web.  doi:10.1021/cm401466r.

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                    Kalland, Liv-Elisif, Magrasó, Anna, Mancini, Alessandro, Tealdi, Cristina, Malavasi, Lorenzo, & Pavia). Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study.  United States.  https://doi.org/10.1021/cm401466r

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                    Kalland, Liv-Elisif, Magrasó, Anna, Mancini, Alessandro, Tealdi, Cristina, Malavasi, Lorenzo, and Pavia). 2013.  
        "Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study".  United States.  https://doi.org/10.1021/cm401466r.

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@article{osti_1088573,

  title        = {Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study},

  author       = {Kalland, Liv-Elisif and Magrasó, Anna and Mancini, Alessandro and Tealdi, Cristina and Malavasi, Lorenzo and Pavia)},

  abstractNote = {Lanthanum tungstate (La28–xW4+xO54+δ) is a good proton conductor and exhibits a complex fluorite-type structure. To gain further understanding of the short-range order in the structure we correlate the optimized configurations obtained by density functional theory (DFT) with the experimental atomic pair distribution function analysis (PDF) of time-of-flight neutron and synchrotron X-ray data, collected at room temperature. The local atomic arrangements cannot be described by means of any average symmetric structure. Tungsten forms WO6 octahedra in alternating directions, La1 is mainly 8-fold coordinated in relatively symmetric cubes, and La2 is coordinated with 6 or 7 oxygens in heavily distorted cubes. Both DFT and PDF confirm that the excess tungsten (x) is incorporated in La2 (1/4, 1/4, 1/4) sites in the La27W5O55.5 composition. This additional tungsten can be considered as a donor self-dopant in the material and has implications to the conducting properties and the defect structure.},

  doi          = {10.1021/cm401466r},

  url          = {https://www.osti.gov/biblio/1088573},
  journal      = {Chemistry of Materials},

  issn         = {0897-4756},

  number       = (11) ; 06, 2013,

  volume       = 25,

  place        = {United States},

  year         = {Wed Oct 02 00:00:00 EDT 2013},

  month        = {Wed Oct 02 00:00:00 EDT 2013}

}

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Title: Local Structure of Proton-Conducting Lanthanum Tungstate La28-xW4+xO54+δ: a Combined Density Functional Theory and Pair Distribution Function Study

Abstract

Citation Formats

Title: Local Structure of Proton-Conducting Lanthanum Tungstate La_28-xW_4+xO_54+δ: a Combined Density Functional Theory and Pair Distribution Function Study