[en] Standard Landau theory coupled to infinitesimal strain allows a concise description of the temperature-driven ferroelectric tetragonal-to-cubic phase transition in PbTiO3 at ambient pressure. Unfortunately, it fails to cover its high-pressure counterpart at ambient temperature. For example, the experimental transition pressure is vastly underestimated and neither the change from first to second order with increasing pressure nor the unusual pressure dependence of the tetragonal unit cell parameters observed in experiment are reproduced. Here we demonstrate that a combination of density functional theory and a recently constructed finite-strain extension of Landau theory provides a natural mechanism for resolving these discrepancies between theory and experiment. Our approach also allows us to determine the full tetragonal-cubic phase boundary in the (P,T) plane including an estimate of the tricritical point. We show that a careful analysis of the thermal elastic baseline is an essential ingredient to the success of this theory.
[University of Luxembourg > Rectorate >]
