First-principles study of the multi-mode anti-ferroelectric transition of PbZrO3

We have studied ab initio the phase transition in PbZrO3, a perovskite oxide usually presented as the prototypic anti-ferroelectric material. Our work reveals the crucial role that anti-ferrodistortive modes – involving concerted rotations of the oxygen octahedra in the structure – play in the transformation, as they select the observed anti-ferroelectric phase, among competing structural variants, via a cooperative trilinear coupling.