Low-temperature anharmonicity of barium titanate: A path-integral molecular-dynamics study

We investigate the influence of quantum effects on the dielectric and piezoelectric properties of barium titanate in its (low-temperature) rhombohedral phase, and show the strongly anharmonic character of this system even at low temperature. For this purpose, we perform path-integral molecular-dynamics simulations under fixed pressure and fixed temperature, using an efficient Langevin thermostat-barostat, and an effective Hamiltonian derived from first-principles calculations. The quantum fluctuations are shown to significantly enhance the static dielectric susceptibility (approximate to by a factor of 2) and the piezoelectric constants, reflecting the strong anharmonicity of this ferroelectric system even at very low temperature. The slow temperature-evolution of the dielectric properties observed below approximate to 100 K is attributed (i) to zero-point energy contributions and (ii) to harmonic behavior if the quantum effects are turned off. DOI: 10.1103/PhysRevB.87.014113