First-principles calculation of the 17O NMR parameters of a calcium aluminosilicate glass

Magali Benoit, Mickaël Profeta, Francesco Mauri, Chris J. Pickard, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

We have computed the 17O NMR parameters of an amorphous calcium aluminosilicate (CAS) from first-principles. The atomic coordinates of a CAS glass of composition (CaO) 0.21(Al 2O 3) 0.12(SiO 2) 0.67 were obtained by quenching a liquid to room temperature by the means of ab initio molecular-dynamics simulations of the Car-Parrinello type. The structure of the glass is found to be overall in good agreement with diffraction experiments. Some excess nonbridging O (NBO) atoms are found and are compensated by tricluster O atoms, i.e., by 3-fold coordinated O atoms to 4-fold coordinated Al or Si atoms. The glass coordinates were used to compute the 17O NMR parameters using GGA-DFT and a correction of the Ca 3d orbital energy. The chemical shifts and the electric field gradients were obtained with the gauge including projector augmented-wave (GIFAW) and the projector augmented-wave (PAW) methods, respectively. The simulated 2D-3QMAS NMR spectrum of the CAS glass is in very good agreement with the available experimental data, notably because it takes into account the disorder present in the glass. This agreement further validates our CAS glass model. We show that the oxygen triclusters are not visible in a 2D-3QMAS NMR 17O spectrum since their NMR parameters overlap with those of the Al-O-Si, Si-O-Si, or Al-O-Al sites. Finally, correlations between the structural characteristics and the values of the NMR parameters are extracted from the calculation with the aim of helping the interpretation of NMR spectra of glasses of similar compositions.

Original languageEnglish (US)
Pages (from-to)6052-6060
Number of pages9
JournalJournal of Physical Chemistry B
Volume109
Issue number13
DOIs
StatePublished - Apr 7 2005

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Aluminosilicates
calcium
Calcium
Nuclear magnetic resonance
Glass
nuclear magnetic resonance
glass
Atoms
projectors
atoms
Chemical shift
calcium aluminosilicate
Chemical analysis
Discrete Fourier transforms
Gages
chemical equilibrium
Molecular dynamics
Quenching
Railroad cars
Diffraction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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First-principles calculation of the 17O NMR parameters of a calcium aluminosilicate glass. / Benoit, Magali; Profeta, Mickaël; Mauri, Francesco; Pickard, Chris J.; Tuckerman, Mark.

In: Journal of Physical Chemistry B, Vol. 109, No. 13, 07.04.2005, p. 6052-6060.

Research output: Contribution to journalArticle

Benoit, Magali ; Profeta, Mickaël ; Mauri, Francesco ; Pickard, Chris J. ; Tuckerman, Mark. / First-principles calculation of the 17O NMR parameters of a calcium aluminosilicate glass. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 13. pp. 6052-6060.
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AB - We have computed the 17O NMR parameters of an amorphous calcium aluminosilicate (CAS) from first-principles. The atomic coordinates of a CAS glass of composition (CaO) 0.21(Al 2O 3) 0.12(SiO 2) 0.67 were obtained by quenching a liquid to room temperature by the means of ab initio molecular-dynamics simulations of the Car-Parrinello type. The structure of the glass is found to be overall in good agreement with diffraction experiments. Some excess nonbridging O (NBO) atoms are found and are compensated by tricluster O atoms, i.e., by 3-fold coordinated O atoms to 4-fold coordinated Al or Si atoms. The glass coordinates were used to compute the 17O NMR parameters using GGA-DFT and a correction of the Ca 3d orbital energy. The chemical shifts and the electric field gradients were obtained with the gauge including projector augmented-wave (GIFAW) and the projector augmented-wave (PAW) methods, respectively. The simulated 2D-3QMAS NMR spectrum of the CAS glass is in very good agreement with the available experimental data, notably because it takes into account the disorder present in the glass. This agreement further validates our CAS glass model. We show that the oxygen triclusters are not visible in a 2D-3QMAS NMR 17O spectrum since their NMR parameters overlap with those of the Al-O-Si, Si-O-Si, or Al-O-Al sites. Finally, correlations between the structural characteristics and the values of the NMR parameters are extracted from the calculation with the aim of helping the interpretation of NMR spectra of glasses of similar compositions.

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