Instability of the layered orthorhombic post-perovskite phase of SrTiO$_3$ and other candidate orthorhombic phases under pressure

Abstract

While the tetragonal antiferro-electrically distorted (AFD) phase with space group $I4/mcm$ is well known for SrTiO$_3$ to occur below 105 K, there are also some hints in literature of an orthorhombic phase, either at lower temperature at high pressure. A previously proposed orthorhombic layered structure of SrTiO$_3$, known as the post-perovskite or CaIrO$_3$ structure with space group $Cmcm$ is shown to have significantly higher energy than the cubic or tetragonal phase and to have its minimum volume at larger volume than cubic perovskite. It thus cannot correspond to a high-pressure phase of SrTiO$_3$. We also study an alternative $Pnma$ phase obtained by two octahedral rotations about different axes. This phase is found to have slightly lower energy than the $I4/mcm$ phase in spite of the fact that its parent, in-phase tilted $P4/mbm$ phase is not found to occur. Alternative ferro-electric tetragonal and orthorhombic structures are also considered. These are not found to occur in our zero temperature calculations but have been suggested in previous literature to occur at higher temperature.