Premium
Pressure‐Induced Intersite BiM (M=Ru, Ir) Valence Transitions in Hexagonal Perovskites
Author(s) -
Huang Zixin,
Auckett Josie E.,
Blanchard Peter E. R.,
Kennedy Brendan J.,
Miiller Wojciech,
Zhou Qingdi,
Avdeev Maxim,
Johnson Mark R.,
Zbiri Mohamed,
Garbarino Gaston,
Marshall William G.,
Gu Qinfen,
Ling Chris D.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201311159
Subject(s) - ionic radius , valence (chemistry) , chemistry , hexagonal crystal system , crystallography , ionic bonding , ab initio , radius , ion , computer security , organic chemistry , computer science
Pressure‐induced charge transfer from Bi to Ir/Ru is observed in the hexagonal perovskites Ba 3+ n BiM 2+ n O 9+3 n ( 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) MM bonds contribute to the finely balanced nature of their electronic states.