Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 141, Issue 11, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4895967
Keywords
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Funding
- U.S. Office of Naval Research [N00014-11-1-0664]
- National Science Foundation [OCI-1053575]
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The compositional dependence of metal-oxygen BO6 octahedral distortions, including bond elongations and rotations, is frequently discussed in the ABO(3) perovskite literature; structural distortions alleviate internal stresses driven by under-or over-coordinated bond environments. Here we identify the dependence of octahedral rotations from changes in metal-oxygen bond covalency in orthorhombic perovskites. Using density functional theory we formulate a covalency metric, which captures both the real and k-space interactions between the magnitude and sense, i.e., in-phase or out-of-phase, octahedral rotations, to explore the link between the ionic-covalent Fe-O bond and the interoctahedral Fe-O-Fe bond angles in Pbnm ferrates. Our survey finds that the covalency of the metal-oxygen bond is correlated with the rotation amplitude: We find the more covalent the Fe-O bond, the less distorted is the structure and the more important the long-range inter-octahedral (Fe-O-Fe bond angle) interactions. Finally, we show how to indirectly tune the B-O bond covalency by A-cation induced BO6 rotations independent of ionic size, facilitating design of targeted bonding interactions in complex perovskites. (C) 2014 AIP Publishing LLC.
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