NMR comparative study of PbMg_1/3Nb_2/3O_3 and PbSc_1/2Nb_1/2O_3 local structure

Abstract

The 93Nb and 45Sc NMR spectra in PbSc_1/2Nb_1/2O_3 (PSN) and PbMg_1/3Nb_2/3O_3 (PMN) disordered relaxor ferroelectrics at the temperature T > T_0 (T_0 is the temperature of the dielectric susceptibility maximum) have been studied. Spectra analysis was performed on the base both of the analytical description of NMR lines shapes, allowing for homogeneous and inhomogeneous broadening related to a random distribution of the electric field gradients and numerical Monte Carlo method taking into account electric field gradients originated from random distribution of Mg, Sc and Nb ions (which may be shifted or not) over B-type cation sites. The observed 1/2 -1/2 transition spectrum both of the 93Nb and 45Sc nuclei in the PSN was shown to contain a narrow (3-4 kHz) almost isotropic part and a broad strongly anisotropic part. These two components of NMR spectra are related to 1:1 Sc/Nb ordered and compositionally disordered regions of the crystal, respectively. It was shown that in the disordered regions Sc^3+, Nb^5+ and O^2- ions are shifted from their cubic lattice sites at one of three possible directions: <100>, <110> or <111>. In PMN the NMR spectrum of 93Nb contains practically only the broad component. The portion of unbroadened spectrum that may correspond to ideal 1:2 regions accounts only for 1-2 percent of the total integral intensity. No evidance was obtained about existence of the 1:1 regions in PMN. The NMR data demonstrate that in PMN the cubic symmetry at T > T_0 is locally broken due to ions shifts similar to that in disordered PSN. The values of the ion shifts were estimated in the point charges point dipoles approximation of the electric field gradients calculation both in the PSN and PMN.