DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Hernández-Laguna, A. and Escamilla-Roa, E. and Timón, V. and Dove, M. T. and Sainz-Díaz, C. I. (2006) DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates. Physics and Chemistry of Minerals, 33 (10). pp. 655-666. DOI https://doi.org/10.1007/s00269-006-0120-z

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Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al3+ by Mg2+ or Fe3+, tetrahedral substitution of Si4+ by Al3+, and different interlayer cations (IC) (Na+, K+, Ca2+, and Mg2+). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe3+ and dispersion tendency of Mg2+ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.

Item Type: Article
Uncontrolled Keywords: 2006 AREP IA52 2006 P
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Physics and Chemistry of Minerals
Volume: 33
Page Range: pp. 655-666
Identification Number: https://doi.org/10.1007/s00269-006-0120-z
Depositing User: Sarah Humbert
Date Deposited: 16 Feb 2009 13:02
Last Modified: 23 Jul 2013 10:07
URI: http://eprints.esc.cam.ac.uk/id/eprint/374

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