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

TL;DR

This study uses first-principles calculations to investigate the phase transition in PbZrO3, highlighting the importance of anti-ferrodistortive modes and their coupling in stabilizing the anti-ferroelectric phase.

Contribution

It provides a detailed ab initio analysis revealing the role of anti-ferrodistortive modes in the anti-ferroelectric transition of PbZrO3, a novel insight into the structural mechanism.

Findings

Anti-ferrodistortive modes are crucial in the phase transition.

These modes involve rotations of oxygen octahedra.

A cooperative trilinear coupling stabilizes the anti-ferroelectric phase.

Abstract

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.