Octahedral Rotation Preferences in Perovskite Iodides and Bromides

Joshua Young, James M. Rondinelli

Research output: Contribution to journalArticlepeer-review

116 Scopus citations

Abstract

Phase transitions in ABX3 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 = Cl, Br, or I), several of which undergo an unusual displacive transition to a tetragonal phase exhibiting in-phase rotations about one axis (a0a0c+ 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.

Original languageEnglish (US)
Pages (from-to)918-922
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume7
Issue number5
DOIs
StatePublished - Mar 3 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Materials Science
  • Physical and Theoretical Chemistry

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