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Title: The structural diversity of ABS{sub 3} compounds with d{sup 0} electronic configuration for the B-cation

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 ABS{sub 3} (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{sup 0} electronic configuration. Our findings indicate that none of these AB combinations prefer a perovskite ground state with corner-sharing BS{sub 6} 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:
; ; ; ;  [1]
  1. The Makineni Theoretical Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, Pennsylvania 19104-6323 (United States)
Publication Date:
OSTI Identifier:
22420105
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 22; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 97 MATHEMATICAL METHODS AND COMPUTING; AMBIENT TEMPERATURE; APPROXIMATIONS; CATIONS; DENSITY FUNCTIONAL METHOD; ELECTRONEGATIVITY; ELECTRONIC STRUCTURE; FREE ENERGY; GROUND STATES; PEROVSKITE