First-principles calculations of solid-state 17O and 29Si NMR spectra of Mg2SiO4 polymorphs

Ashbrook, S. E. and Le Polles, L. and Pickard, C. J. and Berry, A. J. and Wimperis, S. and Farnan, I. (2007) First-principles calculations of solid-state 17O and 29Si NMR spectra of Mg2SiO4 polymorphs. Physical Chemistry Chemical Physics, 9 (13). pp. 1587-1598. DOI

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The nuclear magnetic resonance (NMR) shielding and electric field gradient (EFG) tensors of three polymorphs of Mg2SiO4, forsterite (-Mg2SiO4), wadsleyite (-Mg2SiO4) and ringwoodite (-Mg2SiO4), have been calculated using a density functional theory (DFT) approach with a planewave basis set and pseudopotential approximation. These Mg2SiO4 polymorphs are the principal components of the Earth down to depths of 660 km and have been proposed as the hosts of water in the Earths upper mantle and transition zone. A comparison of our calculations with single-crystal spectroscopic data in the literature for the -polymorph, forsterite, shows that both the magnitude and orientation of the shielding and EFG tensors for O and Si can be obtained with sufficient accuracy to distinguish subtle differences in atomic positions between published structures. We compare calculated 17O MAS NMR quadrupolar powder lineshapes directly with experimental lineshapes and show that we are able to reproduce them within the precision with which the NMR parameters may be determined from multi-parameter fitting. The relatively small amounts of sample available for the - and -polymorphs, arising from the high pressures required for synthesis, has hindered the extraction of NMR parameters in previous work. The application of DFT calculations to these high-pressure polymorphs confirms previous spectral assignments, and provides deeper insight into the empirical correlations and observations reported in the literature. These first-principles methods are highly promising for the determination of local bonding in more complex materials, such as the hydrated forms of Mg2SiO4, by aiding analysis of their multinuclear NMR spectra.

Item Type: Article
Uncontrolled Keywords: 2007 AREP IA54 2007 P
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Physical Chemistry Chemical Physics
Volume: 9
Page Range: pp. 1587-1598
Identification Number:
Depositing User: Sarah Humbert
Date Deposited: 16 Feb 2009 13:01
Last Modified: 23 Jul 2013 10:01

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