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Time-of-flight neutron powder diffraction with milligram samples: the crystal structures of NaCoF

DOI: 10.1107/S1600576714021803 DOI Help

Authors: Alex Lindsay-scott (University College London) , David Dobson (University College London) , Fabrizio Nestola (University of Padova) , Matteo Alvaro (University of Padova) , Nicola Casati (Paul Scherrer Institute) , Christian Liebske (Swiss Federal Institute of Technology) , Kevin S. Knight (ISIS) , Ronald I. Smith (Merck Research Laboratories) , Ian G. Wood (University College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of Applied Crystallography , VOL 47 , PAGES 1939 - 1947

State: Published (Approved)
Published: December 2014

Abstract: Using the recently upgraded Polaris diffractometer at the ISIS Spallation Neutron Source (Rutherford Appleton Laboratory), the crystal structures of the post-perovskite polymorphs of NaCoF3 and NaNiF3 have been determined by time-of-flight neutron powder diffraction from samples, of mass 56 and 16 mg, respectively, recovered after synthesis at 20 GPa in a multi-anvil press. The structure of post-perovskite NaNiF3 has also been determined by single-crystal synchrotron X-ray diffraction for comparison. All measurements were made at atmospheric pressure and room temperature. Despite the extremely small sample size in the neutron diffraction study, there is very good agreement between the positional parameters for NaNiF3 obtained from the refinements of the X-ray and neutron data. Relative to the commonly used oxide post-perovskite analogue phases having calcium as the A cation, the axial ratios and derived structural parameters of these fluoride post-perovskites are more consistent with those of Mg0.91Fe0.09SiO3 at high pressure and temperature. The structures of NaCoF3 and NaNiF3 are very similar, but the unit-cell and CoF6 octahedral volumes of NaCoF3 are larger than the corresponding quantities in NaNiF3, which supports the hypothesis that the Co2+ ion has a high-spin state in this compound. The anisotropic atomic displacement parameters of the Na ions in NaNiF3 post-perovskite are of similar magnitude to those of the F ions. The probability ellipsoid of the F1 ion is a prolate spheroid with its largest component parallel to the b axis of the unit cell, corresponding to rotational motion of the NiF6 octahedra about the a axis of the crystal. Although they must be synthesized at pressures above about 18 GPa, these ABF3 compounds are strongly metastable at atmospheric pressure and room temperature and so are highly suitable for use as analogues for (Mg,Fe)SiO3 post-perovskite in the deep Earth, with significant advantages over oxides such as CaIrO3 or CaPtO3.

Journal Keywords: NaCoF3; NaNiF3; MgSiO3; post-perovskites; perovskites; crystal structure; neutron powder diffraction; single-crystal X-ray diffraction

Subject Areas: Chemistry


Instruments: I15-Extreme Conditions

Added On: 14/01/2015 13:39

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