The structural diversity of ABS3 compounds with d 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 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 BS 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.

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Molecular dynamics simulations of point/line defect structures and oxygen diffusion mechanism in yttrium-doped barium zirconate

“…0.95≤t≤1.05 [30] , 可见两个体系都保持立方晶型的稳定 α 0 值采用4.256 Å [25] . Bulk体系的D v 在4.71×10 -8~6 .84×10 -7 cm 2 s -1 之间, 而 D i s l 体 系 的 D v 略 微 偏 高 , 为 5 .…”