First-principles study on negative thermal expansion of PbTiO3

It is well known that perovskite-type PbTiO3 behaves negative thermal expansion in a wide temperature range from room temperature to Curie temperature (763 K). The present study reports the first-principles study of the anisotropic thermal expansion of PbTiO3, in the framework of the density-functional theory and the density-functional perturbation theory. The curve of temperature dependence of the unit cell volume is presented from 20 to 520K through the calculation of the minimum of total free energy at each temperature point. The negative thermal expansion of PbTiO3 is calculated without empirical parameters. Furthermore, the distinctive thermodynamic act of PbTiO3 from expanding to contracting at tetragonal phase is reproduced. The ab-initio calculations reveal that this unique appearance depends on the phonon vibration. The dynamical contributions of various atoms are also calculated to account for the disparate role of Pb-O and Ti-O bond. (C) 2013 AIP Publishing LLC.