Ab initio statistical mechanics of the ferroelectric phase transition in PbTiO3

Abstract

An effective Hamiltonian for the ferroelectric transition in PbTiO3 is constructed from first-principles density-functional-theory total-energy and linear-response calculations through the use of a localized, symmetrized basis set of ``lattice Wannier functions.'' Explicit parametrization of the polar lattice Wannier functions is used for subspace projection, addressing the issues of LO-TO splitting and coupling to the complementary subspace. In contrast with ferroelectric BaTiO3 and KNbO3, we find significant involvement of the Pb atom in the lattice instability. Monte Carlo simulations for this Hamiltonian show a first-order cubic-tetragonal transition at 660 K. Resulting temperature dependence of spontaneous polarization, c/a ratio and unit-cell volume near the transition are in good agreement with experiment. Comparison of Monte Carlo results with mean field theory analysis shows that both strain and fluctuations are necessary to produce the first order character of this transition.