Polycrystalline samples of the garnets Li 3+x Nd 3 Te 2-x Sb x O 12 have been prepared by high temperature solid state synthesis. X-ray and neutron powder diffraction data show that all compounds crystallize in the space group Ia3 j d with lattice parameters in the range 12.55576(12) Å for x ) 0.05 to 12.6253(2) Å for x ) 1.5. The lithium is distributed over a mixture of oxide tetrahedra and heavily distorted octahedra. Increasing the lithium content in these compounds leads to the introduction of vacancies onto the tetrahedral position and an increasing concentration of lithium found in the octahedra. The latter exhibit considerable positional disorder with two lithium cations positions within each octahedron. Impedance measurements show fast ion conduction with an activation energy of ca. 0.59(6) eV that is largely invariant with composition. Solid-state Li NMR measurements indicate that there is no exchange of lithium between the different coordination environments. These results indicate that lithium conduction in the garnet structure occurs exclusively via a network of edge-linked distorted oxide octahedra and that the tetrahedrally coordination lithium plays no part in the transport properties.
A routinely used assumption when interpreting two-dimensional NMR spectra obtained with a commonly used double-quantum (DQ) magic-angle-spining (MAS) pulse sequence referred to as the refocused incredible natural abundance double-quantum transfer experiment (INADEQUATE) [A. Lesage, M. Bardet, and L. Emsley, J. Am. Chem. Soc. 121, 10987 (1999)] has been that correlation peaks are only observed for pairs of nuclei with a through-bond connectivity. The validity of this assumption is addressed here by theory, experiment, and computer simulations. If the isotropic chemical shifts of the two nuclei are different and the MAS frequency is far from rotational resonance, the theoretical description demonstrates that DQ correlation peaks are indeed indicative of a J coupling. However, if the isotropic chemical shifts are the same, it is shown that DQ peaks can appear for pairs of nuclei even in the absence of a through-bond J coupling. These peaks appear in the specific case of a pair of nuclei with a nonzero through-space dipole-dipole coupling and chemical shift anisotropy tensors having different principal magnitudes or orientations, provided that the MAS frequency is comparable to or smaller than the chemical shift anisotropies. Experimental 31P spectra recorded on a sample of TiP2O7 and computer simulations show that the magnitude of these anomalous peaks increases with increasing B0 magnetic field and that they decrease with increasing MAS frequency. This behavior is explained theoretically.
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