Structure prediction of ordered and disordered multiple octahedral cation perovskites using SPuDS

The software package SPuDS has previously been shown to accurately predict crystal structures of AMX(3) and A(1-x)A'xMX3 perovskites that have undergone octahedral tilting distortions. This paper describes the extension of this technique and its accuracy for A(2)MM'X-6 ordered double perovskites with the aristotype Fmm cubic structure, as well as those that have undergone octahedral tilting distortions. A survey of the literature shows that roughly 70% of all ordered double perovskites undergo octahedral tilting distortions. Of the 11 distinct types of octahedral tilting that can occur in ordered perovskites, five tilt systems account for similar to 97% of the reported structures. SPuDS can calculate structures for the five dominant tilt systems, Fm (3) over barm (a(0)a(0)a(0)), I4/ m (a(0)a(0)c(-)), R (3) over bar (a(-)a(-)a(-)), I2/m (a(0)b(-)b(-)) and P2(1)/n (a(-)a(-)b(+)), as well as two additional tilt systems, Pn (3) over bar (a(+) a(+) a(+)) and P4/ mnc (a(0)a(0)c(+)). Comparison with reported crystal structures shows that SPuDS is quite accurate at predicting distortions driven by octahedral tilting. The favored modes of octahedral tilting in ordered double perovskites are compared and contrasted with those in AMX(3) perovskites. Unit- cell pseudosymmetry in Srand Ca-containing double perovskites is also examined. Experimentally, Sr2MM'O-6 compounds show a much stronger tendency toward pseudosymmetry than do Ca2MM'O-6 compounds with similar tolerance factors.