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Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy


Zimmermann,  H.
Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Max Planck Society;

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Beerwerth, J., Storek, M., Greim, D., Lueg, J., Siegel, R., Cetinkaya, B., et al. (2018). Two-site jumps in dimethyl sulfone studied by one- and two-dimensional 17O NMR spectroscopy. Journal of Magnetic Resonance, 288, 84-94. doi:10.1016/j.jmr.2018.01.016.

Polycrystalline dimethyl sulfone is studied using central-transition oxygen-17 exchange NMR. The quadrupolar and chemical shift tensors are determined by combining quantum chemical calculations with line shape analyses of rigid-lattice spectra measured for stationary and rotating samples at several external magnetic fields. Quantum chemical computations predict that the largest principal axes of the chemical shift anisotropy and electrical field gradient tensors enclose an angle of about 73°. This prediction is successfully tested by comparison with absorption spectra recorded at three different external magnetic fields. The experimental one-dimensional motionally narrowed spectra and the two-dimensional exchange spectrum are compatible with model calculations involving jumps of the molecules about their two-fold symmetry axis. This motion is additionally investigated by means of two-time stimulated-echo spectroscopy which allows for a determination of motional correlation functions over a wider temperature range than previously reported using carbon and deuteron NMR. On the basis of suitable second-order quadrupolar frequency distributions, sin-sin stimulated-echo amplitudes are calculated for a two-site model in the limit of vanishing evolution time and compared with experimental findings. The present study thus establishes oxygen-17 NMR as a powerful method that will be particularly useful for the study of solids and liquids devoid of nuclei governed by first-order anisotropies.