Absence of High-Pressure Ground-State Reentrant Ferroelectricity in PbTiO_{3}

We study ferroelectricity in the classic perovskite ferroelectric PbTiO_{3} to high pressures with density functional theory (DFT) and experimental diamond-anvil techniques. We use second harmonic generation spectroscopy to detect lack of inversion symmetry. Consistent with early understanding and experiments, we find that ferroelectricity disappears at moderate pressures. However, DFT computations show that the disappearance arises from the overtaking of zone boundary instabilities, and not from the squeezing out of the off-centering ferroelectric displacements with pressure, as previously thought. Moreover, at high pressures the distorted perovskite phases are metastable with respect to a new dense centrosymmetric postperovskite phase with P2_{1}/m symmetry and 8-coordinated Ti, which becomes stable at about 70 GPa.