The structural diversity of AB S3 compounds with d 0 electronic configuration for the B -cation

John A. Brehm, Joseph W. Bennett, Michael Rutenberg Schoenberg, Ilya Grinberg, Andrew M. Rappe

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We use first-principles density functional theory within the local density approximation to ascertain the ground state structure of real and theoretical compounds with the formula ABS3 (A = K, Rb, Cs, Ca, Sr, Ba, Tl, Sn, Pb, and Bi; and B = Sc, Y, Ti, Zr, V, and Nb) under the constraint that B must have a d0 electronic configuration. Our findings indicate that none of these AB combinations prefer a perovskite ground state with corner-sharing BS6 octahedra, but that they prefer phases with either edge- or face-sharing motifs. Further, a simple two-dimensional structure field map created from A and B ionic radii provides a neat demarcation between combinations preferring face-sharing versus edge-sharing phases for most of these combinations. We then show that by modifying the common Goldschmidt tolerance factor with a multiplicative term based on the electronegativity difference between A and S, the demarcation between predicted edge-sharing and face-sharing ground state phases is enhanced. We also demonstrate that, by calculating the free energy contribution of phonons, some of these compounds may assume multiple phases as synthesis temperatures are altered, or as ambient temperatures rise or fall.

Original languageEnglish
Article number224703
JournalJournal of Chemical Physics
Issue number22
StatePublished - 14 Jun 2014
Externally publishedYes


FundersFunder number
Air Force Office of Scientific ResearchFA9550-10-1-0248
National Science FoundationDMR11-24696
Office of Naval ResearchN00014-12-1-1033


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