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Ab initio calculations of relative stabilities of different structural arrangements in dioctahedral phyllosilicates

Published online by Cambridge University Press:  01 January 2024

Daniel Tunega
Institute for Theoretical Chemistry, University of Vienna, Währingerstrasse 17, A-1090 Vienna, Austria Department of Environmental Research, Austrian Research Centers GmbH — ARC, A-2444 Seibersdorf, Austria
Bernard A. Goodman*
Department of Environmental Research, Austrian Research Centers GmbH — ARC, A-2444 Seibersdorf, Austria Department of Natural Resources and Environmental Sciences, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA
Georg Haberhauer
Department of Environmental Research, Austrian Research Centers GmbH — ARC, A-2444 Seibersdorf, Austria
Thomas G. Reichenauer
Department of Environmental Research, Austrian Research Centers GmbH — ARC, A-2444 Seibersdorf, Austria
Martin H. Gerzabek
Institute of Soil Research, University of Natural Resources and Applied Life Sciences, Peter-Jordan-Strasse 82b, A-1190 Vienna, Austria
Hans Lischka
Institute for Theoretical Chemistry, University of Vienna, Währingerstrasse 17, A-1090 Vienna, Austria
*E-mail address of corresponding author:


An ab initio theoretical approach has been used to calculate optimized geometries and the relative energies of various compositional arrangements in structures of dioctahedral smectites based on models consisting of two unit-cells. These calculations indicate that the energy differences between structures having vacancies in sites with cis- or trans-OH coordination are small and that their relative energies vary with the chemical nature of the substitutions. For example, a cis-OH coordination for the vacancy was the most stable when the interlayer charge originated from substitution of Al for Si in the tetrahedral sheet, whereas the trans-coordination was the more stable for most cases of substitution in the octahedral sheet, an exception being Fe(II) for Al where the cis-OH coordination was favored. It seems likely, therefore, that long-range structural disorder will be a common phenomenon in natural phyllosilicate specimens.

Research Article
Copyright © 2007, The Clay Minerals Society

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