Understanding correlations in BaZrO3:Structure and dynamics on the nano-scale

TL;DR

This study uses molecular dynamics simulations with machine-learned potentials to analyze the local and global structure of BaZrO3, revealing dynamic fluctuations and phase transitions consistent with experimental observations.

Contribution

It provides new insights into the nanoscale dynamics and phase behavior of BaZrO3, highlighting the role of soft phonon modes and pressure-induced phase transitions.

Findings

Weak diffuse superlattice reflections at low temperature and ambient pressure.

Absence of static nanodomains, but presence of soft dynamic fluctuations.

Phase transition from cubic to tetragonal at around 16 GPa.

Abstract

Barium zirconate BaZrO3 is one of few perovskites that is claimed to retain an average cubic structure down to 0K at ambient pressure, while being energetically very close to a tetragonal phase obtained by condensation of a soft phonon mode at the R-point. Previous studies suggest, however, that the local structure of BaZrO3 may change at low temperature forming nanodomains or a glass-like phase. Here, we investigate the global and local structure of BaZrO3 as a function of temperature and pressure via molecular dynamics simulations using a machine-learned potential with near density functional theory (DFT) accuracy. We show that the softening of the octahedral tilt mode at the R-point gives rise to weak diffuse superlattice reflections at low temperatures and ambient pressure, which are also observed experimentally. However, we do not observe any static nanodomains but rather soft dynamic fluctuations of the ZrO6 octahedra with a correlation length of 2 to 3nm over time-scales of about 1ps. This soft dynamic behaviour is the precursor of a phase transition and explains the emergence of weak superlattice peaks in measurements. On the other hand, when increasing the pressure at 300K we find a phase transition from the cubic to the tetragonal phase at around 16GPa, also in agreement with experimental studies.