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

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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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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