27Al NMR spectroscopy at multiple magnetic fields and ab initio quantum modeling for kaolinite
-
Bing Zhou
and
Tao Wang
Abstract
Diffraction methods indicate clearly that there are two crystallographic Al sites in kaolinite with different site symmetry. Many unsuccessful attempts have been made to resolve the two different Al sites in kaolinite by magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy since the early 1980s. This study attempts to resolve these sites, derive accurate quadrupolar coupling parameters at the two sites, and explain the reasons for the lack of separation by combining NMR spectroscopy at various fields with ab initio quantum modeling.
At a high field such as 21.06 T, large chemical shift anisotropy and dipolar effects can overwhelm the quadrupolar interaction effects for sites with relatively small Cq values such as the two Al sites in kaolinite. The spectra will then display featureless lineshapes lacking the typical quadrupolar interaction characteristics. At lower fields, such as 4.68 T, the quadrupolar interaction effects become dominant, but due to the similarity of the two Al environments in kaolinite, as well as broadening by residual dipole-dipole and chemical shift anisotropy, the 27Al MAS NMR peaks still could not be separated.
To resolve the two different Al sites spectroscopically, 27Al MAS NMR experiments at multiple magnetic fields, satellite transition NMR, and multiple-quantum MAS techniques have been utilized. Although these NMR experiments failed to resolve the two Al sites, the spectra have been interpreted with the aid of theoretical ab initio quantum mechanical modeling using full potential linearized augmented plane wave (FP-LAPW) model and the CASTEP software program. Average values of Cq, η, and δiso for the two Al sites were constrained to be 2.6 MHz, 0.75 and 6.25 ppm with high confidence.
© 2015 by Walter de Gruyter Berlin/Boston
Articles in the same Issue
- 27Al NMR spectroscopy at multiple magnetic fields and ab initio quantum modeling for kaolinite
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- Spectroscopic characteristics of synthetic olivine: An integrated multi-wavelength and multi-technique approach
- Effects of hydration on thermal expansion of forsterite, wadsleyite, and ringwoodite at ambient pressure
- Forsterite, hydrous and anhydrous wadsleyite and ringwoodite (Mg2SiO4): 29Si NMR results for chemical shift anisotropy, spin-lattice relaxation, and mechanism of hydration
- Structural transitions and electron transfer in coffinite, USiO4, at high pressure
- Fe-Mg partitioning between perovskite and ferropericlase in the lower mantle
- Primitive oxygen-isotope ratio recorded in magmatic zircon from the Mid-Atlantic Ridge
- Determination of the potential for extrinsic color development in natural colorless quartz
- X-ray diffraction and Raman spectroscopic study of clinopyroxenes with six-coordinated Si in the Na(Mg0.5Si0.5)Si2O6-NaAlSi2O6 system
- Phase behavior of protoenstatite at high pressure studied by atomistic simulations
- Metasomatic replacement of inherited metamorphic monazite in a biotite-garnet granite from the Nízke Tatry Mountains, Western Carpathians, Slovakia: Chemical dating and evidence for disequilibrium melting
- Shear viscosity and diffusion in liquid MgSiO3: Transport properties and implications for terrestrial planet magma oceans
- Polarized infrared spectroscopic study of diffusion of water molecules along structure channels in beryl
- The vibrational spectrum of lizardite-1T [Mg3Si2O5(OH)4] at the Γ point: A contribution from an ab initio periodic B3LYP calculation
- Origins of Mount St. Helens cataclasites: Experimental insights
- The crystal structure and hydrogen bonding of synthetic konyaite, Na2Mg(SO4)2·5H2O
- Joëlbruggerite, Pb3Zn3(Sb5+,Te6+)As2O13(OH,O), the Sb5+ analog of dugganite, from the Black Pine mine, Montana
- Cathodoluminescence characterization of tridymite and cristobalite: Effects of electron irradiation and sample temperature
- Sequential extraction and DXRD applicability to poorly crystalline Fe- and Al-phase characterization from an acid mine water passive remediation system
- Thermoelasticity of ε-FeSi to 8 GPa and 1273 K
- Demicheleite-(Cl), BiSCl, a new mineral from La Fossa crater, Vulcano, Aeolian Islands, Italy
- Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals
- Evidence for residual elastic strain in deformed natural quartz
- Mineralogy of mine waste at the Vermont Asbestos Group mine, Belvidere Mountain, Vermont
- Structural parameters of chromite included in diamond and kimberlites from Siberia: A new tool for discriminating ultramafic source
- Structure determination of the 2.5 hydrate MgSO4 phase by simulated annealing
Articles in the same Issue
- 27Al NMR spectroscopy at multiple magnetic fields and ab initio quantum modeling for kaolinite
- The effect of oxygen fugacity on the olivine to wadsleyite transformation: Implications for remote sensing of mantle redox state at the 410 km seismic discontinuity
- Spectroscopic characteristics of synthetic olivine: An integrated multi-wavelength and multi-technique approach
- Effects of hydration on thermal expansion of forsterite, wadsleyite, and ringwoodite at ambient pressure
- Forsterite, hydrous and anhydrous wadsleyite and ringwoodite (Mg2SiO4): 29Si NMR results for chemical shift anisotropy, spin-lattice relaxation, and mechanism of hydration
- Structural transitions and electron transfer in coffinite, USiO4, at high pressure
- Fe-Mg partitioning between perovskite and ferropericlase in the lower mantle
- Primitive oxygen-isotope ratio recorded in magmatic zircon from the Mid-Atlantic Ridge
- Determination of the potential for extrinsic color development in natural colorless quartz
- X-ray diffraction and Raman spectroscopic study of clinopyroxenes with six-coordinated Si in the Na(Mg0.5Si0.5)Si2O6-NaAlSi2O6 system
- Phase behavior of protoenstatite at high pressure studied by atomistic simulations
- Metasomatic replacement of inherited metamorphic monazite in a biotite-garnet granite from the Nízke Tatry Mountains, Western Carpathians, Slovakia: Chemical dating and evidence for disequilibrium melting
- Shear viscosity and diffusion in liquid MgSiO3: Transport properties and implications for terrestrial planet magma oceans
- Polarized infrared spectroscopic study of diffusion of water molecules along structure channels in beryl
- The vibrational spectrum of lizardite-1T [Mg3Si2O5(OH)4] at the Γ point: A contribution from an ab initio periodic B3LYP calculation
- Origins of Mount St. Helens cataclasites: Experimental insights
- The crystal structure and hydrogen bonding of synthetic konyaite, Na2Mg(SO4)2·5H2O
- Joëlbruggerite, Pb3Zn3(Sb5+,Te6+)As2O13(OH,O), the Sb5+ analog of dugganite, from the Black Pine mine, Montana
- Cathodoluminescence characterization of tridymite and cristobalite: Effects of electron irradiation and sample temperature
- Sequential extraction and DXRD applicability to poorly crystalline Fe- and Al-phase characterization from an acid mine water passive remediation system
- Thermoelasticity of ε-FeSi to 8 GPa and 1273 K
- Demicheleite-(Cl), BiSCl, a new mineral from La Fossa crater, Vulcano, Aeolian Islands, Italy
- Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals
- Evidence for residual elastic strain in deformed natural quartz
- Mineralogy of mine waste at the Vermont Asbestos Group mine, Belvidere Mountain, Vermont
- Structural parameters of chromite included in diamond and kimberlites from Siberia: A new tool for discriminating ultramafic source
- Structure determination of the 2.5 hydrate MgSO4 phase by simulated annealing
