Analysis of soft optical modes in hexagonal BaTiO3: transference of perovskite local distortions

Abstract

We have performed detailed first-principles calculations to determine the eigenvectors of the zone-center modes of hexagonal BaTiO3 and shown that the experimentally relevant low-energy modes (including the non-polar instability) can be represented as suitable combinations of basic local polar distortions associated with the instability of the cubic perovskite phase. The hexagonal structure provides a testing ground for the analysis of the influence of the stacking of TiO6 octahedra: the occurrence of relatively high-energy chains of dipoles highlights the importance of local effects related to the coherent hybridization enhancement between Ti and O ions. Our results provide simple heuristic rules that could be useful for the analysis of related compounds.