Free energies of ferroelectric crystals from a microscopic approach

TL;DR

This paper presents a microscopic approach using molecular dynamics and thermodynamic integration to compute the free energy of barium titanate near its Curie temperature, aligning well with phenomenological models.

Contribution

It introduces a method to calculate free energy landscapes of ferroelectric crystals from first principles, incorporating constrained polarization states and analyzing supercell size effects.

Findings

Good agreement with Landau potentials at small supercells

Free energy curves are insensitive to supercell size from 12 to 16

Identifies phase separation at low temperature and low polarization

Abstract

The free energy of barium titanate is computed around the Curie temperature as a function of polarization from the first-principles derived effective hamiltonian of Zhong, Vanderbilt and Rabe [Phys. Rev. Lett. 73, 1861 (1994)], through Molecular Dynamics simulations coupled to the method of the Thermodynamic Integration. The main feature of this approach is to calculate the gradient of the free energy in the 3-D space (Px,Py,Pz) from the thermal averages of the forces acting on the local modes, that are obtained by Molecular Dynamics under the constraint of fixed P. A careful analysis of the states of constrained polarization is performed at T=280 K (~ 15-17 K below Tc) especially at low order parameter. These states are found reasonably homogeneous for small supercell size (L=12 and L=16), until inhomogeneous states are observed at low order parameter for large supercells (L=20). However, for reasonable supercell sizes (L=12), the free energy curves obtained are in very good agreement with phenomenological Landau potentials of the litterature. Moreover, the free energy obtained is quite insensitive to the supercell size from L=12 to L=16 at T=280 K, suggesting that interfacial contributions, if any, are negligible at these sizes around Tc. The method allows a numerical estimation of the free energy barrier separating the paraelectric from the ferroelectric phase at Tc. However, our tests evidence phase separation at low temperature and low order parameter, in agreement with the results of Tr\"oster et al [Phys. Rev. B 72 (2005), 094103].