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Octahedral Rotation Preferences in Perovskite Iodides and Bromides
Journal article   Peer reviewed

Octahedral Rotation Preferences in Perovskite Iodides and Bromides

Joshua Young and James M. Rondinelli
The journal of physical chemistry letters, v 7(5), pp 918-922
03 Mar 2016
PMID: 26899936

Abstract

Chemistry Chemistry, Physical Materials Science Materials Science, Multidisciplinary Nanoscience & Nanotechnology Physical Sciences Physics Physics, Atomic, Molecular & Chemical Science & Technology Science & Technology - Other Topics Technology
Phase transitions in ABX(3) perovskites are often accompanied by rigid rotations of the corner-connected BX6 octahedral network. Although the mechanisms for the preferred rotation patterns of perovskite oxides are fairly well recognized, the same cannot be said of halide variants (i.e., X = CI, Br, or I), several of which undergo an unusual displacive transition to a tetragonal phase exhibiting in-phase rotations about one axis (a(0)a(0)c(+) in Glazer notation). To discern the chemical factors stabilizing this unique phase, we investigated a series of 12 perovskite bromides and iodides using density functional theory calculations and compared them with similar oxides. We find that in-phase tilting provides a better arrangement of the larger bromide and iodide anions, which minimizes the electrostatic interactions, improves the bond valence of the A-site cations, and enhances the covalency between the A-site metal and Br- or I- ions. The opposite effect is present in the oxides, with out-of-phase tilting maximizing these factors.

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Collaboration types
Domestic collaboration
Web of Science research areas
Chemistry, Physical
Materials Science, Multidisciplinary
Nanoscience & Nanotechnology
Physics, Atomic, Molecular & Chemical
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