Structural principles of cation ordering and octahedral tilting in A-site ordered double perovskites: ferroelectric CaMnTiO as a model system.

We have used quantum chemical methods to study the structural principles and energetics of A-site ordered AA'BO double perovskites. 33 combinations of A-site ordering and Glazer tilting have been systematically studied for the ferroelectric CaMnTiO model system. The used approach was able to predict the correct combination of A-site ordering and tilting of octahedra in comparison to the experimentally known CaMnTiO. The energy differences between the various combinations of A-site ordering and tilt systems show a large variation of tens of kJ mol per formula unit, which suggests that the methodology used here can be used as a starting point for making reliable predictions on the structures of yet unknown A-site ordered double perovskites. The energy differences due to A-site ordering and octahedral tilting were larger compared to the energy difference arising from ferroelectric distortion in CaMnTiO. The energy differences between various hypothetical double perovskite structures could be explained by studying their structural characteristics in detail. The relative energies are closely correlated with the Mn-O distances and Mn coordination in the studied structures.