Observation of hidden magnesium: First-principles calculations and 25Mg solid-state NMR of enstatite

Abstract

25Mg NMR parameters have been determined for two polymorphs of enstatite (MgSiO3), an important magnesium silicate phase present as a major component of the Earths upper mantle. The crystal structures of both polymorphs contain two crystallographically distinct magnesium sites; however, only a single resonance is observed in 25Mg MAS NMR spectra recorded at 14.1 and 20.0 T. First-principles calculations performed on geometry-optimised crystal structures reveal that the quadrupolar interaction for the second site is expected to be very large, resulting in extensive broadening of the spectral resonance, explaining its apparent absence in the NMR spectrum. 25Mg QCPMG NMR experiments employing variable offset cumulative spectroscopy (VOCS) are used to observe the broadened site and enable measurement of NMR parameters. The large difference in quadrupolar interaction between the two crystallographic magnesium sites is rationalised qualitatively in terms of the distortion of the local coordination environment as well as longer-range effects using a simple point charge model.