Abstract
We conducted powder neutron diffraction for δ-AlOOH samples with and without Mg and Si ions under ambient conditions in order to investigate the long-standing problem of the symmetry of this phase. The observed reflection conditions clearly show that the space group of pure δ-AlOOH is P21 nm with ordered hydrogen bonds, whereas that of δ-(Al0.86Mg0.07Si0.07)OOH is Pnnm or Pnn2 with disordered hydrogen bonds. It is more likely that the space group of δ-(Al0.86Mg0.07Si0.07)OOH is Pnnm, because cation or hydrogen ordering that breaks the mirror plane perpendicular to c axis in the Pnnm structure would not occur. The previously reported inconsistency for the space group of this phase was caused by the substitution of Mg and Si ions to Al site, i.e., the disordered cations with different valences may fluctuate hydrogen positions, and the disordered hydrogen causes the symmetry change.
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Acknowledgments
We thank Dr. Thomas C. Hansen and Dr. John S. Loveday for their help with the neutron diffraction experiments, and Dr. A. Shimojuku for sample syntheses. Prof. E. Ohtani provided access to the Kawai-type high-pressure apparatus at Tohoku University. We also thank Prof. Y. Kudoh for providing information on his study and for fruitful discussions. Figure 1 was drawn by the VESTA program (Momma and Izumi 2008). This study was financially supported by a Grant-in-Aid for Creative Scientific Research entitled ‘Material sciences at ultra-high pressure using the strongest spallation neutron source’ (19GS0205) and also supported by a Global COE program from a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) and MEXT Grant No. 21840024 to KK.
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Komatsu, K., Sano-Furukawa, A. & Kagi, H. Effects of Mg and Si ions on the symmetry of δ-AlOOH. Phys Chem Minerals 38, 727–733 (2011). https://doi.org/10.1007/s00269-011-0445-0
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DOI: https://doi.org/10.1007/s00269-011-0445-0