First-Principles Study of the Electronic Structure and Spontaneous Polarization of PbZr0.4Ti0.6O3
Density functional theory plane-wave pseudopotential with the general gradient approximation (GGA) was used to investigate electronic structural properties and the bulk spontaneous polarization (Ps) of PbZr0.4Ti0.6O3. It is found that there are strong hybridizations between Ti 3d states or Zr 4d states and O 2p states, which can reduce short-range repulsion in atoms and enhance the stability of the ferroelectric phase of PbZr0.4Ti0.6O3. Compared with cubic ideal structure, the calculated internal electronic structural data indicate that the slightly distorted O6 octahedrons around the central Ti and Zr atoms change to the Ti-O5 and Zr-O5 pyramid in the optimized structure, respectively. The major contribution to the spontaneous polarization along  comes from the stronger interaction along the c axis between the Ti and O rather than the Zr and O ions. The Pb atom’s relative displacement of oxygen octahedral implies that the Pb-O bonding interaction is also a key factor impacting the ferroelectricity of PbZr0.4Ti0.6O3. A theoretical spontaneous polarization of 0.78 C/m2 was computed in the tetragonal PbZr0.4Ti0.6O3 along  direction, consistent with the single crystal experimental data.
Yansheng Yin and Xin Wang
Q. X. Zhao et al., "First-Principles Study of the Electronic Structure and Spontaneous Polarization of PbZr0.4Ti0.6O3", Advanced Materials Research, Vols. 79-82, pp. 1249-1252, 2009