An ab initio calculation of 17O and 29Si NMR parameters for SiO2 polymorphs

Research output: Contribution to journalArticle

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Abstract

Ab initio molecular orbital calculations (Hartree-Fock, HF and density functional theories, DFTs) have been carried out for SiO2 polymorphs coesite, low cristobalite, and α-quartz, in order to investigate the reliability of this method for predicting 29Si and 17O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the 29Si and 17O chemical shifts (δiSi and δiO), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δiSi and δiO have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δiSi values agree well (within ±1 ppm) with experimental data. The calculated 17O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δiO for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting 29Si and 17O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.

Original languageEnglish
Pages (from-to)245-259
Number of pages15
JournalSolid State Nuclear Magnetic Resonance
Volume16
Issue number4
DOIs
Publication statusPublished - Jul 2000

Fingerprint

Silicates
Polymorphism
Shells (structures)
Nuclear magnetic resonance
Orbital calculations
nuclear magnetic resonance
Quartz
silicates
Chemical shift
Molecular orbitals
Silicon
Silicon Dioxide
coesite
Density functional theory
Molecular dynamics
Crystal structure
Electric fields
Oxygen
Crystalline materials
chemical equilibrium

Keywords

  • Ab initio
  • Cluster
  • Crystal structure
  • NMR
  • SiO polymorph

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Electronic, Optical and Magnetic Materials

Cite this

An ab initio calculation of 17O and 29Si NMR parameters for SiO2 polymorphs. / Xue, Xianyu; Kanzaki, Masami.

In: Solid State Nuclear Magnetic Resonance, Vol. 16, No. 4, 07.2000, p. 245-259.

Research output: Contribution to journalArticle

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abstract = "Ab initio molecular orbital calculations (Hartree-Fock, HF and density functional theories, DFTs) have been carried out for SiO2 polymorphs coesite, low cristobalite, and α-quartz, in order to investigate the reliability of this method for predicting 29Si and 17O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the 29Si and 17O chemical shifts (δiSi and δiO), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δiSi and δiO have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δiSi values agree well (within ±1 ppm) with experimental data. The calculated 17O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δiO for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting 29Si and 17O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.",
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