Characterization of the Binary Nitrides VN and ScN by Solid-State NMR Spectroscopy

NMR spectra of polycrystalline samples of the binary nitrides ScN and VN were acquired under magic-angle spinning. The observed nuclides Sc-45, V-51 and N-14 are all quadrupolar nuclei with a spin I>1/2 ${I\char62 1/2}$ . However, due to the high symmetry of their rock-salt type structures, the spectra of the nitrides do not exhibit effects of quadrupolar or other anisotropic interactions of significant magnitude. This allows a relatively straightforward evaluation of the acquired spectra, leading to isotropic chemical shift values (delta(iso)) of -213 ppm ((VN)-V-51), 378 ppm ((VN)-N-14), 290 ppm ((ScN)-Sc-45) and 442 ppm ((ScN)-N-14) against commonly used reference standards. In the wider context of N-14-NMR of binary nitrides, it is shown that the distance of nitrogen to the nearest neighbour cation can be correlated to the observed chemical shift

Characterisation of contact twinning for cerussite, PbCO3, by single-crystal NMR spectroscopy

<jats:title>Abstract</jats:title><jats:p>Cerussite, <jats:inline-formula><jats:alternatives><jats:tex-math>$$\\hbox {PbCO}_3$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:msub> <mml:mtext>PbCO</mml:mtext> <mml:mn>3</mml:mn> </mml:msub> </mml:math></jats:alternatives></jats:inline-formula>, like all members of the aragonite group, shows a tendency to form twins, due to high pseudo-symmetry within the crystal structure. We here demonstrate that the twin law of a cerussite contact twin may be established using only <jats:inline-formula><jats:alternatives><jats:tex-math>$$^{207}$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:msup> <mml:mrow /> <mml:mn>207</mml:mn> </mml:msup> </mml:math></jats:alternatives></jats:inline-formula>Pb-NMR spectroscopy. This is achieved by a global fit of several sets of orientation-dependent spectra acquired from the twin specimen, allowing to determine the relative orientation of the twin domains. Also, the full <jats:inline-formula><jats:alternatives><jats:tex-math>$$^{207}$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:msup> <mml:mrow /> <mml:mn>207</mml:mn> </mml:msup> </mml:math></jats:alternatives></jats:inline-formula>Pb chemical shift tensor in cerussite at room temperature is determined from these data, with the eigenvalues being <jats:inline-formula><jats:alternatives><jats:tex-math>$$\\delta _{11} = (-2315\\pm 1)$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:mrow> <mml:msub> <mml:mi>δ</mml:mi> <mml:mn>11</mml:mn> </mml:msub> <mml:mo>=</mml:mo> <mml:mrow> <mml:mo>(</mml:mo> <mml:mo>-</mml:mo> <mml:mn>2315</mml:mn> <mml:mo>±</mml:mo> <mml:mn>1</mml:mn> <mml:mo>)</mml:mo> </mml:mrow> </mml:mrow> </mml:math></jats:alternatives></jats:inline-formula> ppm, <jats:inline-formula><jats:alternatives><jats:tex-math>$$\\delta _{22} = (-2492 \\pm 3)$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:mrow> <mml:msub> <mml:mi>δ</mml:mi> <mml:mn>22</mml:mn> </mml:msub> <mml:mo>=</mml:mo> <mml:mrow> <mml:mo>(</mml:mo> <mml:mo>-</mml:mo> <mml:mn>2492</mml:mn> <mml:mo>±</mml:mo> <mml:mn>3</mml:mn> <mml:mo>)</mml:mo> </mml:mrow> </mml:mrow> </mml:math></jats:alternatives></jats:inline-formula> ppm, and <jats:inline-formula><jats:alternatives><jats:tex-math>$$\\delta _{33} = (-3071 \\pm 3)$$</jats:tex-math><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\"> <mml:mrow> <mml:msub> <mml:mi>δ</mml:mi> <mml:mn>33</mml:mn> </mml:msub> <mml:mo>=</mml:mo> <mml:mrow> <mml:mo>(</mml:mo> <mml:mo>-</mml:mo> <mml:mn>3071</mml:mn> <mml:mo>±</mml:mo> <mml:mn>3</mml:mn> <mml:mo>)</mml:mo> </mml:mrow> </mml:mrow> </mml:math></jats:alternatives></jats:inline-formula> ppm.</jats:p&gt

Correlation of the Isotropic NMR Chemical Shift with Oxygen Coordination Distances in Periodic Solids

In Nuclear Magnetic Resonance (NMR) spectroscopy, the isotropic chemical shift δiso is a measure of the electron density around the observed nuclide. For characterization of solid materials and compounds, it is desirable to find correlations between δiso and structural parameters such as coordination numbers and distances to neighboring atoms. Correlations of good quality are easier to find when the coordination sphere is formed by only one element, as the electron density is obviously strongly dependent on the atomic number. The current study is therefore restricted to nuclides in pure oxygen coordination. It is shown that the isotropic shift δiso correlates well with the average oxygen distances (as defined by the coordination sphere) for the nuclides 23Na (with spin I=3/2), 27Al (I=5/2), and 43Ca (I=7/2), using literature data for a range of periodic solids. It has been previously suggested for 207Pb (I=1/2) that δiso may alternatively be related to the shortest oxygen distance in the structure, and our study corroborates this also for the nuclides considered here. While the correlation with the minimal distance is not always better, it has the advantage of being uniquely defined. In contrast, the average distance is strongly dependent on the designation of the oxygen coordination sphere, which may be contentious in some crystal structures

Correlation of the Isotropic NMR Chemical Shift with Oxygen Coordination Distances in Periodic Solids

In Nuclear Magnetic Resonance (NMR) spectroscopy, the isotropic chemical shift δiso is a measure of the electron density around the observed nuclide. For characterization of solid materials and compounds, it is desirable to find correlations between δiso and structural parameters such as coordination numbers and distances to neighboring atoms. Correlations of good quality are easier to find when the coordination sphere is formed by only one element, as the electron density is obviously strongly dependent on the atomic number. The current study is therefore restricted to nuclides in pure oxygen coordination. It is shown that the isotropic shift δiso correlates well with the average oxygen distances (as defined by the coordination sphere) for the nuclides 23Na (with spin I=3/2), 27Al (I=5/2), and 43Ca (I=7/2), using literature data for a range of periodic solids. It has been previously suggested for 207Pb (I=1/2) that δiso may alternatively be related to the shortest oxygen distance in the structure, and our study corroborates this also for the nuclides considered here. While the correlation with the minimal distance is not always better, it has the advantage of being uniquely defined. In contrast, the average distance is strongly dependent on the designation of the oxygen coordination sphere, which may be contentious in some crystal structures

Determination of the Full 207Pb Chemical Shift Tensor of Anglesite, PbSO4, and Correlation of the Isotropic Shift to Lead–Oxygen Distance in Natural Minerals

The full 207 Pb chemical shift (CS) tensor of lead in the mineral anglesite, PbSO 4 , was determined from orientation-dependent nuclear magnetic resonance (NMR) spectra of a large natural single crystal, using a global fit over two rotation patterns. The resulting tensor is characterised by the reduced anisotropy Δ δ = ( - 327 ± 4 ) ppm, asymmetry η C S = 0 . 529 ± 0 . 002 , and δ i s o = ( - 3615 ± 3 ) ppm, with the isotropic chemical shift δ i s o also verified by magic-angle spinning NMR on a polycrystalline sample. The initially unknown orientation of the mounted single crystal was included in the global data fit as well, thus obtaining it from NMR data only. By use of internal crystal symmetries, the amount of data acquisition and processing for determination of the CS tensor and crystal orientation was reduced. Furthermore, a linear correlation between the 207 Pb isotropic chemical shift and the shortest Pb–O distance in the co-ordination sphere of Pb 2 + solely surrounded by oxygen has been established for a large database of lead-bearing natural minerals