Dynamic stabilization of perovskites at elevated temperatures: A comparison between cubic BaFeO$_{\textbf{3}}$ and vacancy-ordered monoclinic BaFeO$_{\textbf{2.67}}$

TL;DR

This study uses ab initio simulations to compare the dynamic stability of cubic BaFeO3 and vacancy-ordered BaFeO2.67, revealing that both are stabilized above 130 K despite initial harmonic instabilities, with vacancies having limited impact on stabilization temperature.

Contribution

It provides the first detailed comparison of vacancy effects on the dynamic stability of BaFeO3 perovskites using ab initio molecular dynamics.

Findings

Both structures are stabilized above 130 K.

Ordered vacancies do not significantly change the stabilization temperature.

Strong anharmonicity observed near vacancies above critical temperature.

Abstract

The impact of ordered vacancies on the dynamic stability of perovskites is investigated under the $\textit{ab initio}$ framework with a focus on cubic BaFeO$_{3}$ ($Pm\bar{3}m$) and vacancy-ordered monoclinic BaFeO$_{2.67}$ ($P2_{1}/m$). The harmonic approximation shows that both structures are dynamically unstable at 0 K. For the monoclinic structure, the instability is related to rotational distortions of the Fe coordination tetrahedra near the ordered vacancies. $\textit{Ab initio}$ molecular dynamics simulations in combination with the introduced structural descriptor demonstrate that both structures are stabilized above 130 K. Our results suggest that the ordered vacancies do not significantly alter the critical temperature at which Ba$-$Fe$-$O perovskites are dynamically stabilized. Further, strong anharmonicity for the vacancy-ordered structure above its critical temperature is revealed by a significant asymmetry of the trajectories of O anions near the ordered vacancies.