Ferroelectric Phase Transition in Barium Titanate Revisited with Ab Initio Molecular Dynamics

The ferroelectric phase transition of the perovskite barium titanate as well as its technical importance regarding the switching of respective polar properties is well known and has been thoroughly studied, both experimentally and on theoretical grounds. While details about the phase diagram as well as transition temperatures are experimentally well known, the theoretical approaches still face difficulties in contributing a detailed description of these phase transitions. Within this work, a new methodological approach is introduced to revisit the ferroelectric phase transition with first-principles methods. With the chosen ab initio molecular dynamics (AIMD) method in combination with the applied NpT ensemble, we are able to join the accuracy of density functional theory (DFT) with ambient conditions, realized using a thermostat and barostat in an MD simulation. The derived phase diagram confirms recent corrections in the theoretical models and reproduces the phase boundary pressure dependence of TC. In conclusion of the statistical atomistic dynamics, the nature of the transition can be described in a more detailed way. In addition, this work paves the way towards locally patterned piezoelectrica by means of acoustic standing waves as well as piezoelectrically induced acoustic resonators.