Date Awarded


Document Type


Degree Name

Doctor of Philosophy (Ph.D.)




Various experimental and theoretical work indicate that the local structure and chemical ordering play a crucial role in the different physical behaviors of lead-based complex ferroelectrics with the ABO 3 perovskite structure. First-principles linearized augmented plane wave (LAPW) with the local orbital extension method within local density approximation (LDA) are performed on structural models of Pb(Zr1/2Ti1/2 )O3 (PZT), Pb(Sc1/2Ta1/2)O3 (PST), Pb(Sc2/3W1/3)O3 (PSW), and Pb(Mg 1/3Nb2/3)O3 (PMN) to calculate electric field gradients (EFGs). In order to simulate these disordered alloys, various structural models were constructed with different imposed chemical orderings and symmetries. Calculations were carried out as a function of B-site chemical ordering, applied strain, and imposed symmetry. Large changes in the EFGs are seen in PZT as the electric polarization rotates between the tetragonal and rhombohedral directions. The onset of polarization rotation in monoclinic Cm symmetry strongly correlates with the shearing of the TiO6 octahedron, and there is a sharp change in slope in plots of Ti EFGs versus octahedral distortion index. The same changes in EFGs and the BO6 shearing corresponding to the change of off-centering direction are also seen in PST. In PSW and PMN, the calculated B cation EFGs showed more sensitivity to the surrounding nearest B neighboring environments. Calculated B atom EFGs in all alloys are considerably larger than those inferred from the NMR measurements. Based on comparisons with experiments, the calculated results are interpreted in terms of static and dynamic structural models of these materials.



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