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The high-temperature polymorphs of K3AlF6.

Graham King1, Artem M Abakumov, Patrick M Woodward

  • 1Lujan Neutron Scattering Center, Los Alamos National Laboratory, MS H805, Los Alamos, New Mexico 87545, USA. gking@lanl.gov

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The crystal structures of three high-temperature potassium hexafluoroaluminate (K(3)AlF(6)) polymorphs were solved. Complex superstructures arise from AlF(6) octahedra tilting, influencing K(+) ion coordination in these perovskite phases.

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Area of Science:

  • Materials Science
  • Crystallography
  • Solid-State Chemistry

Background:

  • Potassium hexafluoroaluminate (K(3)AlF(6)) exhibits multiple high-temperature polymorphs.
  • Understanding these crystal structures is crucial for predicting material properties and phase transitions.

Purpose of the Study:

  • To determine the crystal structures of the beta, gamma, and delta phases of K(3)AlF(6).
  • To elucidate the relationship between AlF(6) octahedra tilting and potassium ion coordination in these polymorphs.

Main Methods:

  • Neutron powder diffraction
  • Synchrotron X-ray powder diffraction
  • Electron diffraction
  • Pair distribution function analysis

Main Results:

  • The beta and gamma phases are complex superstructures of the double-perovskite K(2)KAlF(6) structure, driven by AlF(6) octahedra tilting.
  • Specific tilting patterns in beta and gamma phases lead to varied K(+) ion coordination (pentagonal bipyramidal, 7-fold, or octahedral).
  • The delta phase, while exhibiting a cubic double-perovskite average structure, shows local deviations with large-amplitude octahedra rotations and off-center K(+) displacements.

Conclusions:

  • The high-temperature polymorphs of K(3)AlF(6) display intricate crystal structures derived from the double-perovskite framework.
  • Octahedral tilting and associated K(+) ion displacements are key factors governing the structural complexity and coordination environments in these phases.