High sensitivity of 17O NMR to p-d hybridization in transition metal perovskites: first principles calculations of large anisotropic chemical shielding

TL;DR

This study uses first principles calculations to show that 17O NMR chemical shielding is highly sensitive to p-d hybridization in transition metal perovskites, revealing anisotropic effects and aiding local structure analysis.

Contribution

The paper introduces a first principles embedded cluster approach to accurately calculate 17O chemical shielding tensors in transition metal perovskites, linking NMR shifts to p-d hybridization effects.

Findings

Large anisotropy in chemical shielding tensors observed.

Linear variation of isotropic shielding with B-O-B bond asymmetry.

Good agreement between calculations and experimental NMR data.

Abstract

A first principles embedded cluster approach is used to calculate O chemical shielding tensors, sigma, in prototypical transition metal oxide ABO_3 perovskite crystals. Our principal findings are 1) a large anisotropy of sigma between deshielded sigma_x ~ sigma_y and shielded sigma_z components (z along the Ti-O bond); 2) a nearly linear variation, across all the systems studied, of the isotropic sigma_iso and uniaxial sigma_ax components, as a function of the B-O-B bond asymmetry. We show that the anisotropy and linear variation arise from large paramagnetic contributions to sigma_x and sigma_y due to virtual transitions between O(2p) and unoccupied B(nd) states. The calculated isotropic delta_iso and uniaxial delta_ax chemical shifts are in good agreement with recent BaTiO_3 and SrTiO_3 single crystal 17O NMR measurements. In PbTiO_3 and PbZrO_3, calculated delta_iso are also in good agreement with NMR powder spectrum measurements. In PbZrO_3, delta_iso calculations of the five chemically distinct sites indicate a correction of the experimental assignments. The strong dependence of sigma on covalent O(2p)-B(nd) interactions seen in our calculations indicates that 17O NMR spectroscopy, coupled with first principles calculations, can be an especially useful tool to study the local structure in complex perovskite alloys.