title: The structural diversity of ABS₃ compounds with d⁰ electronic configuration for the B-cation.
abstract: 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 d(0) 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.
authors.affiliation: The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: John A
authors.initials: JA
authors.lastname: Brehm
authors.affiliation: The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Bennett
authors.affiliation: The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Michael Rutenberg
authors.initials: MR
authors.lastname: Schoenberg
authors.affiliation: The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Ilya
authors.initials: I
authors.lastname: Grinberg
authors.affiliation: The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Rappe