Finite-temperature phonon dispersion and vibrational dynamics of BaTiO3 from first-principles molecular dynamics

Abstract

A systematic investigation of the finite-temperature phonon dispersion, including its smearing and temperature effects, is carried out using autocorrelation function method together with first-principles molecular dynamics method along the [001] direction of $\mathrm{Ba}\mathrm{Ti}{\mathrm{O}}_{3}$, as an illustrating example of entropy-stabilized structures. A unique anharmonicity in the cubic phase mainly derived from the interactions between titanium and oxygen atoms is revealed, which provides extremely strong damping and smearing to longitudinal optical phonons but no discernible effect on the shift of phonon energies. The anharmonicity gives rise to a nearly constant density distribution in a cubic region around the equilibrium position of the relative motion of titanium atoms with respect to oxygen atoms. These results may help to gain a further insight into complex interactions in entropy-stabilized structures and provide an essential benchmark reference to the development of the promising machine-learning based molecular dynamics methods for the investigation of phonon properties.