Effects of the antiferrodistortive instability on the structural behavior of BaZrO$_3$ by atomistic simulations

TL;DR

This study uses atomistic simulations to explore how antiferrodistortive instabilities influence the structural behavior of BaZrO$_3$, revealing dynamic local distortions and nanoregions that affect its physical properties.

Contribution

The paper develops a shell model from ab initio calculations and investigates the microscopic effects of AFD instabilities on BaZrO$_3$'s structure at finite temperature.

Findings

Oxygen octahedra show minimal distortion with oscillating rotation angles.

Short-range ordered nanoregions exist regardless of phase transitions.

Simulations support the presence of dynamic, unstable domains in cubic BaZrO$_3$.

Abstract

Recently, the possibility of a low-temperature non-cubic phase in BaZrO$_3$ has generated engaging discussions about its true ground state and the consequences on its physical properties. In this paper, we investigate the microscopic behavior of the BaZrO$_3$ cubic phase by developing a shell model from $ab~initio$ calculations and by performing molecular dynamics simulations at finite temperature and under negative pressure. We study three different scenarios created by tuning the intensities of the antiferrodistortive (AFD) instabilities, and consequently, the sequence of phase transitions with temperature. From a detailed analysis of the cubic phase at atomic scale, we find that oxygen octahedra are barely distorted, present rotation angles that may oscillate with significant amplitudes, are AFD correlated with their closest neighbors on the plane perpendicular to the pseudocubic rotation axis exhibiting $(0 0 a^-)$-type ordering, and form instantaneous, dynamic and unstable domains over time. Our simulations support the existence of nanoregions with short-range ordering in cubic BaZrO$_3$ associated with experimentally observed anomalies and unveil that they can exist regardless of whether or not structural phase transitions related with AFD distortions occur at lower temperatures.