Effects of the antiferrodistortive instability on the structural behavior of BaZrO3 by atomistic simulations

Abstract

Recently, the possibility of a low-temperature noncubic phase in BaZrO3 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 BaZrO3 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 (00a-)-type ordering, and form instantaneous, dynamic, and unstable domains over time. Our simulations support the existence of nanoregions with short-range ordering in cubic BaZrO3 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.