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Realistic molecular cluster models for exfoliated kaolinite

Published online by Cambridge University Press:  02 January 2018

Attila Táborosi  and
Robert K. Szilagyi
Attila Táborosi
Affiliation:
Department of Environmental Engineering, Faculty of Engineering, University of Pannonia, PO Box 10, Veszprém, Hungary
Robert K. Szilagyi*
Affiliation:
Department of Chemistry and Biochemistry, Montana State University, Bozeman, USA
*
3Current address: Department of Analytical Chemistry, Faculty of Engineering, University of Pannonia, PO Box 10, Veszprém, Hungary
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Abstract

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Molecular cluster models, developed for an exfoliated kaolinite, provide a structural description comparable to that of periodic slab models for a fraction of the computational cost. These models include both the octahedral and the tetrahedral sheets of kaolinite. The first-generation model (G1) contains the inner and outer coordination sphere of the Al- and Si-honeycombs as the preferred sites for adsorption of small organic molecules. Since no experimental information is available to date at the atomic level for exfoliated kaolinite, we carried out a systematic density functional theory evaluation for establishing the most reasonable coordinates of the ions and groups. The results of molecular cluster and periodic calculations were utilized for evaluating semi-empirical Hamiltonians on larger models. Using a PM7 Hamiltonian, the structure of cluster models containing 1 + 6 (second generation) and 1 + 6 + 12 (third generation) Al- and Si-honeycombs which are out of reach for ab initio calculations, were determined. These molecular slab models offer a structural platform for adsorption, intercalation and delamination studies.

Keywords

exfoliated kaolinitemolecular cluster modelsnanoclay structure flexibilitysemi-empirical calculationsdensity functional theory
Type
Research Article
Information
Clay Minerals , Volume 50 , Issue 3 , August 2015 , pp. 307 - 327
Creative Commons
Creative Common License - CCCreative Common License - BY
Copyright © The Mineralogical Society of Great Britain and Ireland 2015 This is an Open Access article, distributed under the terms of the Creative Commons Attribution license. (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

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