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Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics

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Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates : Evidence for Proton Dynamics. / Griffin, John M.; Wimperis, Stephen; Berry, Andrew J. et al.

In: The Journal of Physical Chemistry C, Vol. 113, No. 1, 08.01.2009, p. 465-471.

Research output: Contribution to Journal/MagazineJournal articlepeer-review

Harvard

Griffin, JM, Wimperis, S, Berry, AJ, Pickard, CJ & Ashbrook, SE 2009, 'Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics', The Journal of Physical Chemistry C, vol. 113, no. 1, pp. 465-471. https://doi.org/10.1021/jp808651x

APA

Griffin, J. M., Wimperis, S., Berry, A. J., Pickard, C. J., & Ashbrook, S. E. (2009). Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics. The Journal of Physical Chemistry C, 113(1), 465-471. https://doi.org/10.1021/jp808651x

Vancouver

Griffin JM, Wimperis S, Berry AJ, Pickard CJ, Ashbrook SE. Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics. The Journal of Physical Chemistry C. 2009 Jan 8;113(1):465-471. Epub 2008 Dec 5. doi: 10.1021/jp808651x

Author

Griffin, John M. ; Wimperis, Stephen ; Berry, Andrew J. et al. / Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates : Evidence for Proton Dynamics. In: The Journal of Physical Chemistry C. 2009 ; Vol. 113, No. 1. pp. 465-471.

Bibtex

@article{7506a517825a4444b6cbdbea42f801c6,
title = "Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics",
abstract = "First-principles calculations of O-17 quadrupolar and chemical shift NMR parameters were performed using CASTEP, a density functional theory (I)FT) code, to try and interpret high-resolution O-17 NMR spectra of the humite group minerals hydroxyl-chondrodite (2Mg(2)SiO(4)center dot Mg(OH)(2)) and hydroxyl-clinohumite (4Mg(2)SiO(4)center dot Mg(OH)(2)), which are models for the incorporation of water within the Earth's upper mantle. The structures of these humite minerals contain two possible crystallographically inequivalent H sites with 50% occupancy. Isotropic O-17 multiple-quantum magic angle spinning (MQMAS) spectra were therefore simulated using the calculated O-17 NMR parameters and assuming either a static or dynamic model for the positional disorder of the H atoms. Only the dynamic disorder model provided simulated spectra that agree with experimental O-17 MQMAS spectra of hydroxyl-chondrodite and hydroxyl-clinohumite. Previously published O-17 satellite-transition magic angle spinning (STMAS) spectra of these minerals showed significant dynamic line-broadenings in the isotropic frequency dimension. We were able to reproduce these line-broadenings with at least qualitative accuracy using a combination of the same dynamic model for the positional H disorder, calculated values for the change in O-17 quadrupolar NMR parameters upon H exchange, and a simple analytical model for dynamic line-broadening in MAS NMR experiments. Overall, this study shows that a combination of state-of-the-art NMR methodology and first-principles calculations of NMR parameters is able to provide information on dynamic processes in solids with atomic-scale resolution that is unobtainable by any other method.",
keywords = "NOMINALLY ANHYDROUS MINERALS, HIGH-RESOLUTION NMR, QUANTUM MAS NMR, QUADRUPOLAR NUCLEI, 1ST-PRINCIPLES CALCULATIONS, WADSLEYITE BETA-MG2SIO4, MULTIPLE-QUANTUM, CHEMICAL-SHIFTS, MANTLE OLIVINE, EARTHS MANTLE",
author = "Griffin, {John M.} and Stephen Wimperis and Berry, {Andrew J.} and Pickard, {Chris J.} and Ashbrook, {Sharon E.}",
year = "2009",
month = jan,
day = "8",
doi = "10.1021/jp808651x",
language = "English",
volume = "113",
pages = "465--471",
journal = "The Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "1",

}

RIS

TY - JOUR

T1 - Solid-State O-17 NMR Spectroscopy of Hydrous Magnesium Silicates

T2 - Evidence for Proton Dynamics

AU - Griffin, John M.

AU - Wimperis, Stephen

AU - Berry, Andrew J.

AU - Pickard, Chris J.

AU - Ashbrook, Sharon E.

PY - 2009/1/8

Y1 - 2009/1/8

N2 - First-principles calculations of O-17 quadrupolar and chemical shift NMR parameters were performed using CASTEP, a density functional theory (I)FT) code, to try and interpret high-resolution O-17 NMR spectra of the humite group minerals hydroxyl-chondrodite (2Mg(2)SiO(4)center dot Mg(OH)(2)) and hydroxyl-clinohumite (4Mg(2)SiO(4)center dot Mg(OH)(2)), which are models for the incorporation of water within the Earth's upper mantle. The structures of these humite minerals contain two possible crystallographically inequivalent H sites with 50% occupancy. Isotropic O-17 multiple-quantum magic angle spinning (MQMAS) spectra were therefore simulated using the calculated O-17 NMR parameters and assuming either a static or dynamic model for the positional disorder of the H atoms. Only the dynamic disorder model provided simulated spectra that agree with experimental O-17 MQMAS spectra of hydroxyl-chondrodite and hydroxyl-clinohumite. Previously published O-17 satellite-transition magic angle spinning (STMAS) spectra of these minerals showed significant dynamic line-broadenings in the isotropic frequency dimension. We were able to reproduce these line-broadenings with at least qualitative accuracy using a combination of the same dynamic model for the positional H disorder, calculated values for the change in O-17 quadrupolar NMR parameters upon H exchange, and a simple analytical model for dynamic line-broadening in MAS NMR experiments. Overall, this study shows that a combination of state-of-the-art NMR methodology and first-principles calculations of NMR parameters is able to provide information on dynamic processes in solids with atomic-scale resolution that is unobtainable by any other method.

AB - First-principles calculations of O-17 quadrupolar and chemical shift NMR parameters were performed using CASTEP, a density functional theory (I)FT) code, to try and interpret high-resolution O-17 NMR spectra of the humite group minerals hydroxyl-chondrodite (2Mg(2)SiO(4)center dot Mg(OH)(2)) and hydroxyl-clinohumite (4Mg(2)SiO(4)center dot Mg(OH)(2)), which are models for the incorporation of water within the Earth's upper mantle. The structures of these humite minerals contain two possible crystallographically inequivalent H sites with 50% occupancy. Isotropic O-17 multiple-quantum magic angle spinning (MQMAS) spectra were therefore simulated using the calculated O-17 NMR parameters and assuming either a static or dynamic model for the positional disorder of the H atoms. Only the dynamic disorder model provided simulated spectra that agree with experimental O-17 MQMAS spectra of hydroxyl-chondrodite and hydroxyl-clinohumite. Previously published O-17 satellite-transition magic angle spinning (STMAS) spectra of these minerals showed significant dynamic line-broadenings in the isotropic frequency dimension. We were able to reproduce these line-broadenings with at least qualitative accuracy using a combination of the same dynamic model for the positional H disorder, calculated values for the change in O-17 quadrupolar NMR parameters upon H exchange, and a simple analytical model for dynamic line-broadening in MAS NMR experiments. Overall, this study shows that a combination of state-of-the-art NMR methodology and first-principles calculations of NMR parameters is able to provide information on dynamic processes in solids with atomic-scale resolution that is unobtainable by any other method.

KW - NOMINALLY ANHYDROUS MINERALS

KW - HIGH-RESOLUTION NMR

KW - QUANTUM MAS NMR

KW - QUADRUPOLAR NUCLEI

KW - 1ST-PRINCIPLES CALCULATIONS

KW - WADSLEYITE BETA-MG2SIO4

KW - MULTIPLE-QUANTUM

KW - CHEMICAL-SHIFTS

KW - MANTLE OLIVINE

KW - EARTHS MANTLE

U2 - 10.1021/jp808651x

DO - 10.1021/jp808651x

M3 - Journal article

VL - 113

SP - 465

EP - 471

JO - The Journal of Physical Chemistry C

JF - The Journal of Physical Chemistry C

SN - 1932-7447

IS - 1

ER -