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Dynamics on the microsecond timescale in hydrous silicates studied by solid-state H-2 NMR spectroscopy

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<mark>Journal publication date</mark>2010
<mark>Journal</mark>Physical Chemistry Chemical Physics
Issue number12
Number of pages10
Pages (from-to)2989-2998
<mark>Original language</mark>English


Solid-state H-2 NMR spectroscopy has been used to probe the dynamic disorder of hydroxyl deuterons in a synthetic sample of deuterated hydroxyl-clinohumite (4Mg(2)SiO(4)center dot Mg(OD)(2)), a proposed model for the incorporation of water within the Earth's mantle. Both static and magic angle spinning (MAS) NMR methods were used. Static H-2 NMR appears to reveal little evidence of the dynamic process, yielding results similar to those obtained from deuterated brucite (Mg(OD)(2)), where no dynamics on the relevant timescale are expected to be present. However, in H-2 MAS NMR spectra, considerable line broadening is observed for hydroxyl-clinohumite and a H-2 double-quantum (DQ) MAS NMR spectrum confirms that this is due to motion on the microsecond timescale. Using a model for dynamic exchange of the hydroxyl deuterons between two sites identified in previous diffraction studies, first-principles density functional theory (DFT) calculations of H-2 (spin I = 1) quadrupolar NMR parameters, and a simple analytical model for dynamic line broadening in MAS NMR experiments, we were able to reproduce the observed motional line broadening and use this to estimate a rate constant for the dynamic process. From analysis of the observed H-2 linewidths in variable-temperature MAS experiments, an activation energy for the exchange process was also determined. A simulated static H-2 NMR lineshape based on our dynamic model is consistent with the observed experimental static NMR spectrum, confirming that the motion present in this system is not easily detectable using a static NMR approach. Finally, a H-2 DQMAS NMR spectrum of fluorine-substituted H-2-enriched hydroxyl-clinohumite shows how the dynamic exchange process is inhibited by O-D center dot center dot center dot F- hydrogen-bonding interactions.