Landau Theory of Tilting of Oxygen Octahedra in Perovskites

The list of possible commensurate phases obtained from the parent tetragonal phase of Ruddlesden-Popper systems, A${}_{n+1}$B${}_n$C${}_{3n+1}$ for general $n$ due to a single phase transition involving the reorienting of octahedra of C (oxygen) ions is reexamined using a Landau expansion. This expansion allows for the nonlinearity of the octahedral rotations and the rotation-strain coupling. It is found that most structures allowed by symmetry are inconsistent with the constraint of rigid octahedra which dictates the form of the quartic terms in the Landau free energy. For A${}_2$BC${}_4$ our analysis allows only 10 (see Table III) of the 41 structures listed by Hatch {\it et al.} which are allowed by general symmetry arguments. The symmetry of rotations for RP systems with $n>2$ is clarified. Our list of possible structures in Table VII excludes many structures allowed in previous studies.