First-principles calculations of $^{17}$O NMR chemical shielding in Pb(Zr$_{1/2}$Ti$_{1/2}$)O$_3$ and Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$: linear dependence on transition-metal/oxygen bond lengths

Abstract

First-principles density functional theory (DFT) oxygen chemical shift tensors were calculated for A(B,B$^{\prime}$)O$_3$ perovskite alloys Pb(Zr$_{1/2}$Ti$_{1/2}$)O$_3$ (PZT) and Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$ (PMN). Quantum chemistry methods for embedded clusters and the GIPAW method [C.\ J.\ Pickard and F.\ Mauri, {\it Phys. Rev. B} {\bf 63} 245101 (2001)] for periodic boundary conditions were used. Results from both methods are in good agreement for PZT and prototypical perovskites. PMN results were obtained using only GIPAW. Both isotropic $δ_\mathrm{iso}$ and axial $δ_\mathrm{ax}$ chemical shifts were found to vary approximately linearly as a function of the nearest-distance transition-metal/oxygen bond length,$r_\mathrm{s}$. Using these results, we argue against Ti clustering in PZT, as conjectured from recent $^{17}$O NMR magic-angle-spinning measurements. Our findings indicate that $^{17}$O NMR measurements, coupled with first-principles calculations, can be an important probe of local structure in complex perovskite solid solutions.