Si-F bonding in aluminosilicate glasses: Inferences from ab initio NMR calculations
-
Yun Liu
and
Hanna Nekvasil
Abstract
Although it has been well accepted that F-Al linkages dominate in F-bearing alkali aluminosilicate glasses, the possibility of F-Si linkages remains unresolved. Recent 19F NMR results have been interpreted as indicative of not only the presence of the Al-F-Na(n) linkages but also of the presence of Si-F-Na(n) linkages. High level ab initio NMR calculations were performed to investigate the nature of possible species contributing to the 19F spectra.
The B3LYP/6-31G* level was used to optimize structures and a scaling technique applied to the calculation of NMR properties using both HF and B3LYP methods at the 6-311+G(2df,p) level. The applicability of this scaling method was checked by comparing calculated results against experimental data on several crystalline materials; the results are improved over HF or DFT methods alone. The calculation results show that none of the F-Al species investigated can produce the -147 ppm peak of Schaller et al. (1992). However, several species in which F is bonded to fourfold-, fivefold-, and sixfold-coordinated Si produce a 19F chemical shift of approximately -147 ppm. These results verify the assignments of this peak by Zeng and Stebbins (2000) to tetrahedral Si-F and NaSiF6-like species, and rule out many other possible species. Several additional species such as a fivefold coordinated Si-F species may further contribute to the -147 ppm 19F peak.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- Presidential Address. Scales of disequilibrium and rates of equilibration during metamorphism
- Characterization of coexisting NH4- and K-micas in very low-grade metapelites
- Effect of sonic and ultrasonic frequencies on the crystallization of basalt
- Sulfur saturation limits in silicate melts and their implications for core formation scenarios for terrestrial planets
- Molecular water in beryl, VIAl2 [Be3Si6O18]·nH2O, as a function of pressure and temperature: An experimental study
- Fluid-induced nucleation of (Y + REE)-phosphate minerals within apatite: Nature and experiment. Part I. Chlorapatite
- X-ray spectroscopic investigations of fluids in the hydrothermal diamond anvil cell: The hydration structure of aqueous La3+ up to 300 °C and 1600 bars
- Fibrous nanoinclusions in massive rose quartz: HRTEM and AEM investigations
- Polysomatism in högbomite: The crystal structures of 10T, 12H, 14T, and 24R polysomes
- Ordering of hydroxyl defects in hydrous wadsleyite (β-Mg2SiO4)
- The crystal structure and cation ordering of Phase-X-(K1–x–n)2(Mg1–n[Al,Cr]n)2Si2O7H2x: A potential K- and H-bearing phase in the mantle
- Feasibility of determining the quantitative OH content of garnets with Raman spectroscopy
- Raman spectroscopic study of garnet inclusions in diamonds from the mantle transition zone
- Raman spectroscopy of Fe2O3 to 62 GPa
- Study of the (010) olivine surface by Rutherford backscattering spectrometry in channeling geometry
- Equation of state of dense hydrous magnesium silicate phase A, Mg7Si2O8(OH)6
- Si-F bonding in aluminosilicate glasses: Inferences from ab initio NMR calculations
- Monoclinic nearly stoichiometric wüstite at low temperatures
- On the nature of tincalconite
- Letters. Chloride ion sites in silicate and aluminosilicate glasses: A preliminary study by 35Cl solid-state NMR
- Nuclear magnetic resonance and infrared spectroscopic study of excess-boron olenite from Koralpe, Styria, Austria
