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

Literature Information

Publication Date 2010-02-03
DOI 10.1039/B924666E
Impact Factor 3.676
Authors

John M. Griffin, Andrew J. Miller, Andrew J. Berry, Stephen Wimperis, Sharon E. Ashbrook


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Abstract

Solid-state 2H NMR spectroscopy has been used to probe the dynamic disorder of hydroxyl deuterons in a synthetic sample of deuterated hydroxyl-clinohumite (4Mg2SiO4·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 2H 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 2H MAS NMR spectra, considerable line broadening is observed for hydroxyl-clinohumite and a 2H 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 2H (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 2H linewidths in variable-temperature MAS experiments, an activation energy for the exchange process was also determined. A simulated static 2H 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 2H DQMAS NMR spectrum of fluorine-substituted 2H-enriched hydroxyl-clinohumite shows how the dynamic exchange process is inhibited by O–D⋯F− hydrogen-bonding interactions.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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