Physics and Chemistry of Minerals

, Volume 33, Issue 10, pp 655–666 | Cite as

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

  • Alfonso Hernández-Laguna
  • Elizabeth Escamilla-Roa
  • Vicente Timón
  • Martin T. Dove
  • C. Ignacio  Sainz-Díaz
Original Paper


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.


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Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Alfonso Hernández-Laguna
    • 1
  • Elizabeth Escamilla-Roa
    • 1
  • Vicente Timón
    • 1
  • Martin T. Dove
    • 2
  • C. Ignacio  Sainz-Díaz
    • 3
  1. 1.Estación Experimental del ZaidínConsejo Superior de Investigaciones Científicas (CSIC)GranadaSpain
  2. 2.Department of Earth SciencesUniversity of CambridgeCambridgeUK
  3. 3.Instituto Andaluz de Ciencias de la TierraConsejo Superior de Investigaciones Científicas (CSIC)/Universidad de GranadaGranadaSpain

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