Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 5, Pages 918-922Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.6b00094
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Funding
- National Science Foundation [DMR-1454688, DMR-1420620]
- Drexel's University Research Computing Facility
- CARBON cluster at the Center for Nanoscale Materials (Argonne National Laboratory)
- DOE-BES [DE-AC02-06CH11357]
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1454688] Funding Source: National Science Foundation
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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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