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A structural phase-transition in K(Mg1−xCux)F3 perovskite

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Abstract

A complete solid-solution series between cubic (Pm 3 m) KMgF3 and tetragonal (I4/mcm) KCuF3 was synthesized at 730–735 °C in an inert atmosphere. X-ray powder-diffraction at room temperature shows that the transition between the cubic and tetragonal perovskite structures in the series K (Mg1−xCux) F3 occurs at x ∼ 0.6. Rietveld structure-refinements were done for selected compositions. In the cubic phase, all parameters are linear with composition up to the transition point. At the transition point, there is a strong discontinuity in the cell volume; this is strongly anisotropic with expansion along the a axes and contraction along the c axis due to a pronounced axial elongation of the (Mg, Cu) F6 octahedron that increases with increasing Cu content. The phase transition is first-order, with a discontinuity of ≈2% in the symmetry-breaking strain at xC. It is proposed that the phase transition in K (Mg, Cu) F3 is due to the onset of the cooperative Jahn-Teller effect.

Compositional relationships for lattice vibrations in this solid solution were established using thin-film infrared spectroscopy. A phase transition occurring above 60 mole % KCuF3 is indicated by the appearance of one of the two modes expected for the tetragonal phase; the weaker mode is not resolved below 80 mole % KCuF3. Modes common to both structures vary smoothly and continuously across the binary; however, frequencies do not depend linearly on composition, nor is mode-softening discernable. Two-mode behaviour is observed only for the bending motion of the cubic phase, because this peak alone has non-overlapping end-member components.

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References

  • Appleman DE, Evans Jr. HT (1973) Job 9214: indexing and leastsquares refinement of powder diffraction data. U.S. Geol. Surv., Comput. Contrib. 20 NTIS Document PB 2–16 188

  • Baldochi SL, Gesland JY (1992) Crystal-growth of pure and lead doped barium-lithium fluoride. Mater Res Bull 27:891–900

    Google Scholar 

  • Baldochi SL, Mazzocchi VL, Parente CBR, Morato SP (1994) Study of the crystalline quality of Czochralski-grown barium lithium-fluoride single-crystals. Mater Res Bull 29:1321–1331

    Google Scholar 

  • Barker AS, Ditzenberger JA, Guggenheim HJ (1986) Long-wavelength optical lattice vibrations in mixed KMgF3-KNiF3 crystals. Phys Rev 175:1180–1190

    Google Scholar 

  • Bellafrouh K, Daul C, Michelcalendini FM (1992) Superhyperfine structure, optical-spectra and equilibrium geometry for Mn2+ in fluoride hosts. New J Chem 16:1119–1121

    Google Scholar 

  • Boumriche A, Gesland JY, Bulou A, Rousseau M, Fourquet JL, Hennion B (1994) Structure and dynamics of the inverted perovskite BaLiF3. Solid State Comm 91:125–128

    Google Scholar 

  • Carpenter MA (1992) Thermodynamics of phase transitions in minerals: A macroscopic approach. In: Price GD, Ross NL (eds) The stability of minerals, pp. 172–215. Chapman and Hall, London

    Google Scholar 

  • Chang IF, Mitra SS (1968) Application of a modified randomelement-isodisplacement model to long-wave length optic phonons of mixed crystals. Phys Rev 172:924–933

    Google Scholar 

  • Chopelas A, Boehler R (1992) Thermal expansivity in the lower mantle. Geophys Res Lett 19:1983–1986

    Google Scholar 

  • Eby RK, Hawthorne FC (1993) Structural relations in copper oxysalt minerals. I. Structural hierarchy. Acta Cryst B 49:28–56

    Google Scholar 

  • Fowler PW, Ding F, Munn RW (1995) Polarizabilities of anions in anisotropic environments — the fluoride-ion in the perovskite lattices NaMgF3, KMgF3 and KCaF3. Molec Phys 84:787–797

    Google Scholar 

  • Hill RJ, Howard CJ (1986) A computer program for Rietveld analysis of fixed wavelength X-ray and neutron powder diffraction patterns. Australian Atomic Energy Commission (Lucas Heights Research Laboratories, PMB, Sutherland, New South Wales, Australia), Report M 112

    Google Scholar 

  • Hofmeister AM (1995) Infrared microspectroscopy in earth science. In: Humeck HJ (ed) Practical guide to infrared microspectroscopy pp 377–416. Marcel Dekker Inc., New York

    Google Scholar 

  • Hofmeister AM, Billips K (1991) Comparison of infrared reflectance spectra of fluoride perovskites. Spectrochim Acta A47:1607–1617

    CAS  Google Scholar 

  • Hofmeister AM, Xu J, Mao H-K, Bell PM, Hoering TC (1989) Thermodynamics of Fe-Mg olivines at mantle pressures: Midand far-infrared spectroscopy at high pressure. Am Mineral 74:281–306

    Google Scholar 

  • International Tables For X-Ray Crystallography (1974). Vol. IV. Birmingham: Kynoch Press

  • Karamyan AA (1979) Optical vibrations and force field of perovskite cubic-type crystals. Opt Spectrosc 47:389–400

    Google Scholar 

  • Katrusiak A, Ratuszna A (1992) Phase-transitions and the structure of NaMnF3 perovskite crystals as a function of temperature and pressure. Solid State Comm 84:435–441

    Google Scholar 

  • Kauppinen JK, Moffatt DJ, Mantsch HH, Cameron DG (1981) Fourier self-deconvolution: a method for resolving intrinsically overlapped bands. Appl Spectrosc 35:271–276

    CAS  Google Scholar 

  • Lehner N, Rauh H, Strobel K, Geick R, Heger G, Bouillot J, Renker B, Rousseau M, Sterling WG (1982) Lattice dynamics, lattice instabilities and phase transitions in fluoride perovskites. J Phys C Solid State Phys 15:6545–6564

    Google Scholar 

  • Liu L-G (1976) Orthorhombic perovskite phases in olivine, pyroxene and garnet at high pressures and temperatures. Phys Earth Planet Int 11:289–298

    Google Scholar 

  • Maslen EN, Spadaccini N, Ito T, Marumo F, Tanaka K, Satow Y (1993) Synchrotron-radiation study of potassium zinc fluoride. Acta Cryst B 49:632–636

    Google Scholar 

  • McCammon CA, Rubie DC, Ross CR II, Siefert F, O'Neill HSC (1992) Mössbauer spectra of 57Fe0.05Mg0.95SiO3 perovskite at 80 and 298 K. Am Mineral 77:894–897

    Google Scholar 

  • Nakagawa I (1973) Transverse and longitudinal lattice frequencies and interatomic potential in some AMF3 perovskite fluoride crystals. Spectrochim Acta A29:1451–1461

    Google Scholar 

  • Nakamoto K (1978) Infrared and Raman Spectra of Inorganic and Coordination Compounds. John Wiley and Sons, New York 448 p

    Google Scholar 

  • Okazaki A (1967 a) The polytype structures of KCuF3. J Phys Soc Jap 26: 870

    Google Scholar 

  • Okazaki A (1967b) Errata: The polytype structures of KCuF3. J Phys Soc Jap 27:518

    Google Scholar 

  • Perry CH, Young EH (1967) Infrared studies of some perovskite fluorides. I. Fundamental lattice vibrations. J Appl Phys 38:4616–4628

    Google Scholar 

  • Ringwood AE (1989) Significance of the terrestrial Mg/Si ratio. Earth Planet Sci Lett 95:1–7

    Google Scholar 

  • Rodriguez F, Riesen H, Gudel HU (1991) Luminescence properties of Mn2+ in KMgF3 and KZnF3 perovskite. J Lumin 50:101–110

    Google Scholar 

  • Rubins RS, Drumheller JE (1987) The temperature dependence of the EPR spectrum of Cu2+ in ZnTiF6 · 6 H2O between 4 and 160 K. J Chem Phys 86:6660–6664

    Google Scholar 

  • Rubins RS, Tello LN, De DK, Black TD (1984) Jahn-Teller EPR spectra of Cu2+ in MgSiF6 · 6H2O. J Chem Phys 81:4230–4233

    Google Scholar 

  • Schmitz-Dumont O von, Grimm D (1967) Die Lichtabsorption des zweiwertigen Kupfers in binären und ternären Fluoriden. Z Anorg Allg Chem 355:280–294

    Google Scholar 

  • Schofield PF, Redfern SAT (1992) Ferroelastic phase transition in the sanmartinite (ZnWO4)-cuproscheelite (CuWO4) solid solution. J Phys Cond Matt 4:375–388

    Google Scholar 

  • Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst A 32:751–767

    Google Scholar 

  • Stobel K, Geick R (1979) Infrared-active phonons of KMnF3 in both tetragonal phases. J Phys C Solid State Phys 12:3855–3870

    Google Scholar 

  • Stokes HT, Hatch DM (1988) Isotropy Subgroups of the 230 Crystallographic Space Groups. World Scientific, Singapore

    Google Scholar 

  • Tanaka K, Konishi M, Marumo F (1979) Electron density distribution in crystals of KCuF3 with Jahn-Teller distortion. Acta Cryst B 35:1303–1308

    Google Scholar 

  • Toledano J-C, Toledano P (1987) The Landau Theory of Phase Transitions. World Scientific, Singapore

    Google Scholar 

  • Watson GW, Parker SC, Wall A (1992) Molecular-dynamics simulation of fluoride-perovskites. J Phys Cond Matt 4:2097–2108

    Google Scholar 

  • Wiles DB, Young RA (1981) A new computer program for Rietveld analysis of X-ray powder diffraction patterns. J Appl Cryst 14:149–151

    Google Scholar 

  • Wolf GH, Bukowinski MST (1987) Theoretical study of the structural properties and equations of state of MgSiO3 and CaSiO3 perovskites: implications for lower mantle composition. In: Manghnami MH, Syono Y (eds) High pressure research in mineral physics, pp. 313–331. AGU, Washington, D.C.

    Google Scholar 

  • Woolen F (1972) Optical Properlies of Solids. Academic Press, New York City

    Google Scholar 

  • Zhao Y, Weidner DJ, Parise JB, Cox DE (1993 a) Thermal expansion and structural distortion of perovskite — data for NaMgF3 perovskite. Part I. Phys Earth Planet Int 76:1–16

    Google Scholar 

  • Zhao Y, Weidner DJ, Parise JB, Cox DE (1993 b) Critical phenomena and phase transition in perovskite — data for NaMgF3 perovskite. Part II. Phys Earth Planet Int 76:17–34

    Google Scholar 

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Authors and Affiliations

  1. Department of Geological Sciences, University of Manitoba, R3T 2N2, Winnipeg, Manitoba, Canada

    Peter C. Burns & Frank C. Hawthorne

  2. Department of Earth and Planetary Sciences, Washington University in St. Louis, Campus Box 1169, 63130-4899, St. Louis, MO, USA

    Anne M. Hofmeister

  3. Department of Geosciences, Oregon State University, 97331-5506, Corvallis, OR, USA

    Stephanie L. Moret

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  1. Peter C. Burns
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  2. Frank C. Hawthorne
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  3. Anne M. Hofmeister
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  4. Stephanie L. Moret
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Burns, P.C., Hawthorne, F.C., Hofmeister, A.M. et al. A structural phase-transition in K(Mg1−xCux)F3 perovskite. Phys Chem Minerals 23, 141–150 (1996). https://doi.org/10.1007/BF00220725

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  • DOI: https://doi.org/10.1007/BF00220725

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