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Six-fold-coordinated phosphorus by oxygen in AlPO4 quartz homeotype under high pressure

Nature Materials volume 6, pages 698–702 (2007)Cite this article

Abstract

AlPO4 belongs to the berlinite quartz homeotype family, which has been the subject of intense high-pressure research triggered by the supposed existence of reversible pressure-induced amorphization. X-ray diffraction experiments, complemented with ab initio calculations, demonstrate the existence of two high-pressure crystalline polymorphs and show that AlPO4 shares the same two-stage densification mechanism as silica. In the first step, a compact hexagonal sublattice of oxygen atoms is formed. In the second step, the cations redistribute in the interstices giving rise to a monoclinic distorted CaCl2 phase. The most outstanding feature of the phase is that phosphorous becomes six-fold coordinated by oxygen, adopting a configuration unknown so far in solid-state science. This finding opens possibilities in the high-pressure chemistry of phosphorus. The close relationship of AlPO4 with silica suggests the existence of completely unexplored families of compounds analogous to those of six-fold-coordinated silicates but based on PO6.

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Figure 1: ADXRD diffraction spectra under high pressure.
Figure 2: Rietveld refinements.
Figure 3: AlPO4 high-pressure polymorphs.
Figure 4: AlPO4 lattice parameters.
Figure 5: AlPO4 equation of state.
Figure 6: Relative enthalpy of several AlPO4 polymorphs.

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Acknowledgements

We thank M. A. Alario for a critical reading of the manuscript. We acknowledge the Ministerio de Educación y Ciencia of Spain (project BFM2001-3309-C02-01/02). A.M.S. acknowledges the French National Supercomputing Facility IDRIS, where the calculations have been carried out under the projects CP9-61387 and CP9-71387.

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Authors and Affiliations

  1. ICMUV, Universidad de Valencia, c/Dr. Moliner 50, 46100 Burjassot, Valencia, Spain

    Julio Pellicer-Porres

  2. Physique des Milieux Denses, IMPMC, CNRS, Université Pierre et Marie Curie -Paris 6, 140 rue de Lourmel, 75015 Paris, France

    Antonino Marco Saitta & Alain Polian

  3. Synchrotron SOLEIL, L’ Orme des Merisiers, Saint-Aubin, BP 48 91192 Gif-sur-Yvette Cedex, France

    Jean Paul Itié

  4. E.S.R.F., BP 220, 38043 Grenoble Cedex, France

    Michael Hanfland

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Correspondence to Julio Pellicer-Porres.

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Pellicer-Porres, J., Saitta, A., Polian, A. et al. Six-fold-coordinated phosphorus by oxygen in AlPO4 quartz homeotype under high pressure. Nature Mater 6, 698–702 (2007). https://doi.org/10.1038/nmat1966

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