Pressure‐Induced Intersite BiM (M=Ru, Ir) Valence Transitions in Hexagonal Perovskites |
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| Authors: | Zixin Huang Josie E Auckett Dr Peter E R Blanchard Prof Brendan J Kennedy Dr Wojciech Miiller Dr Qingdi Zhou Dr Maxim Avdeev Dr Mark R Johnson Dr Mohamed Zbiri Dr Gaston Garbarino Dr William G Marshall Dr Qinfen Gu Prof Chris D Ling |
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| Affiliation: | 1. School of Chemistry, The University of Sydney, Sydney 2006 (Australia);2. Bragg Institute, ANSTO, Menai 2234 (Australia);3. Institut Laue‐Langevin, BP 156, 38042 Grenoble Cedex 9 (France);4. European Synchrotron Research Facility, BP 220, 38043 Grenoble Cedex 9 (France);5. ISIS Facility, STFC, Rutherford Appleton Laboratory, Didcot OX11 0QX (UK);6. Australian Synchrotron, 800 Blackburn Road, Clayton 3168 (Australia) |
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| Abstract: | Pressure‐induced charge transfer from Bi to Ir/Ru is observed in the hexagonal perovskites Ba3+nBiM2+nO9+3n (n=0,1; M=Ir,Ru). These compounds show first‐order, circa 1 % volume contractions at room temperature above 5 GPa, which are due to the large reduction in the effective ionic radius of Bi when the 6s shell is emptied on oxidation, compared to the relatively negligible effect of reduction on the radii of Ir or Ru. They are the first such transitions involving 4d and 5d compounds, and they double the total number of cases known. Ab initio calculations suggest that magnetic interactions through very short (ca. 2.6 Å) M? M bonds contribute to the finely balanced nature of their electronic states. |
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| Keywords: | ab initio calculations charge transfer high‐pressure chemistry perovskite phases phase transitions |
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