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 ${\delta }_{\mathrm{iso}}$ and axial ${\delta }_{\mathrm{ax}}$ 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.

11 pages, 2 figures

References in corpus (5)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Physics of thin-film ferroelectric oxides
• Local Structure and Macroscopic Properties in PMN-PT and PZN-PT solid solutions
• DFT investigation of 3d transition metal NMR shielding tensors in diamagnetic systems using the gauge-including projector augmented-wave method
• High sensitivity of 17O NMR to p-d hybridization in transition metal perovskites: first principles calculations of large anisotropic chemical shielding

Cited by in corpus (1)

• {\it Ab initio} ${}^{27}Al$ NMR chemical shifts and quadrupolar parameters for $A{l}_2{O}_3$ phases and their precursors