Journal article
Covalent dependence of octahedral rotations in orthorhombic perovskite oxides
The Journal of chemical physics, v 141(11), pp 114704-114704
21 Sep 2014
PMID: 25240365
Abstract
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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Details
- Title
- Covalent dependence of octahedral rotations in orthorhombic perovskite oxides
- Creators
- Antonio Cammarata - Czech Technical University in PragueJames M. Rondinelli - Drexel University
- Publication Details
- The Journal of chemical physics, v 141(11), pp 114704-114704
- Publisher
- American Institute of Physics
- Number of pages
- 10
- Grant note
- OCI-1053575 / National Science Foundation; National Science Foundation (NSF) N00014-11-1-0664 / U.S. Office of Naval Research; Office of Naval Research
- Resource Type
- Journal article
- Language
- English
- Web of Science ID
- WOS:000342843200031
- Scopus ID
- 2-s2.0-84907486996
- Other Identifier
- 991019330797104721
InCites Highlights
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Physical
- Physics, Atomic, Molecular & Chemical