Pressure-induced Intersite Bi—M (M=Ru, Ir) valence transitions in hexagonal perovskites

Zixin Huang, Josie E. Auckett, Peter E. R. Blanchard, Brendan J. Kennedy, Wojciech Miiller, Qingdi Zhou, Maxim Avdeev, Mark R. Johnson, Mohamed Zbiri, Gaston Garbarino, William G. Marshall, Qinfen Gu, Chris D. Ling

Research output: Contribution to journalArticlepeer-review

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.
Original languageEnglish
Pages (from-to)3482-3485
Number of pages4
JournalAngewandte Chemie
Volume126
Issue number13
DOIs
Publication statusPublished - 24 Mar 2014
Externally publishedYes

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