Local structures of polar wurtzites Zn_{1-x}Mg_{x}O studied by Raman and {67}Zn/{25}Mg NMR spectroscopies and by total neutron scattering

Local compositions and structures of Zn_{1-x}Mg_{x}O alloys have been investigated by Raman and solid-state {67}Zn/{25}Mg nuclear magnetic resonance (NMR) spectroscopies, and by neutron pair-distribution-function (PDF) analyses. The E2(low) and E2(high) Raman modes of Zn_{1-x}Mg_{x}O display Gaussian- and Lorentzian-type profiles, respectively. At higher Mg substitutions, both modes become broader, while their peak positions shift in opposite directions. The evolution of Raman spectra from Zn_{1-x}Mg_{x}O solid solutions are discussed in terms of lattice deformation associated with the distinct coordination preferences of Zn and Mg. Solid-state magic-angle-spinning (MAS) NMR studies suggest that the local electronic environments of {67}Zn in ZnO are only weakly modified by the 15% substitution of Mg for Zn. {25}Mg MAS spectra of Zn_{0.85}Mg_{0.15}O show an unusual upfield shift, demonstrating the prominent shielding ability of Zn in the nearby oxidic coordination sphere. Neutron PDF analyses of Zn_{0.875}Mg_{0.125}O using a 2x2x1 supercell corresponding to Zn_{7}MgO_{8} suggest that the mean local geometry of MgO_{4} fragments concurs with previous density functional theory (DFT)-based structural relaxations of hexagonal wurtzite MgO. MgO_{4} tetrahedra are markedly compressed along their c-axes and are smaller in volume than ZnO_{4} units by ~6%. Mg atoms in Zn_{1-x}Mg_{x}O have a shorter bond to the $c$-axial oxygen atom than to the three lateral oxygen atoms, which is distinct from the coordination of Zn. The precise structure, both local and average, of Zn_{0.875}Mg_{0.125}O obtained from time-of-flight total neutron scattering supports the view that Mg-substitution in ZnO results in increased total spontaneous polarization.Comment: 12 pages, 14 figures, 2 table

Chemical shift correlations in disordered solids

We show how two-dimensional chemical shift conditional probability distributions can be extracted from experimental NMR correlation spectra of disordered solids. We show that transverse dephasing times are of central importance in determining the resolution (and sensitivity) of these probability distributions. These conditional probability distributions provide a new source of structural information characteristic of disordered solids, which is much more sensitive to structure than the individual-atom chemical shift distributions. The structural information contained in these distributions is clearly a potentially extremely rich source for understanding disorder. This is illustrated with examples of a phosphorus-containing organic compound and with a sample of disordered cellulose where the different structural allomorphs present are identified from the distributions

NMR measurements of scalar-coupling distributions in disordered solids

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