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DFT calculation of crystallographic properties of dioctahedral 2:1 phyllosilicates

Published online by Cambridge University Press:  09 July 2018

J. Ortega-Castro ,
N. Hernández-Haro ,
A. Hernández-Laguna  and
C. I. Sainz-Díaz
J. Ortega-Castro
Affiliation:
Estación Experimental del Zaidín (CSIC), C. Profesor Albareda, 1, 18008-Granada, Spain
N. Hernández-Haro
Affiliation:
Estación Experimental del Zaidín (CSIC), C. Profesor Albareda, 1, 18008-Granada, Spain
A. Hernández-Laguna
Affiliation:
Estación Experimental del Zaidín (CSIC), C. Profesor Albareda, 1, 18008-Granada, Spain
C. I. Sainz-Díaz*
Affiliation:
Laboratorio de Estudios Cristalográficos, Instituto Andaluz de Ciencias de la Tierra, CSIC, Universidad de Granada, Av. Fuentenueva s/n, 18002-Granada, Spain
*
*E-mail: [email protected]
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Abstract

The low-charge dioctahedral 2:1 phyllosilicates are an important group of clay minerals that have a low degree of cation substitution and very weak interlayer interatomic interactions which are difficult to reproduce with quantum mechanical calculations. In order to study the crystallographic properties of these compounds with density functional theory (DFT) quantum-mechanical methods, an optimization of norm-conserving pseudopotentials of Al, Si, O, H and Na atoms has been carried out, and an optimization of the cutoff radii of the basis sets has been accomplished. Crystallographic properties and vibrational stretching frequencies of the OH groups, ν(OH), have been calculated, being consistent with previous computational and experimental results. All frequencies can be related to the different molecular environment of the OH groups. The effect of octahedral Fe3+ substitution on the ν(OH) frequency is reproduced. Several configurations of cation substitutions and interlayer cation (IC) positions are studied in low-charge dioctahedral 2:1 phyllosilicates, such as Al4(Si7–xAlx)O20(OH)4Nax, with x = 0.25, 0.50 and 0.75, indicating that the IVAl3+ is highly dispersed and the IC tends to be in the substituted ditrigonal hole. For the Al4(Si7Al)O20(OH)4Na composition, the trans-vacant form is more stable than the cis-vacant one.

Keywords

DFTdensity functional theoryphyllosilicatesinterlayer cationslow-charge
Type
Research Article
Information
Clay Minerals , Volume 43 , Issue 3 , September 2008 , pp. 351 - 361
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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References

Anglada, E., Soler, J.M., Junquera, J. & Artacho, E. (2002) Systematic generation of finite-range atomic basis sets for linear-scaling calculations. Physics Review. B66, 205101.CrossRefGoogle Scholar
Artacho, E., Sánchez-Portal, D., Ordejón, P., García, A. & Soler, J.M. (1999) Linear-scaling ab-initio calculations for large and complex systems. Physic Status Solidi, 215, 809–817.3.0.CO;2-0>CrossRefGoogle Scholar
Bachelet, G.B. & Schluter, M. (1982) Relativistic norm-conserving pseudopotentials. Physics Review, B25, 2103-2108.Google Scholar
Besson, G. & Drits, V.A. (1997) Refined relationship between chemical composition of dioctahedral fine-grained micaceous minerals and their infrared spectra within the OH stretching region. Clays and Clay Minerals, 45, 170–183.Google Scholar
Besson, G., Drits, V.A., Dainyak, L.G. & Smoliar, B.B. (1987) Analysis of cation distribution in dioctahedral micaceous minerals on the basis of IR spectroscopy data. Clay Minerals, 11, 465-478.Google Scholar
Bosenick, A., Dove, M.T., Myers, E.R., Palin, E., Sainz-Diaz, C.I., Guiton, B., Warren, M.C., Craig, M.S. & Redfern, S.A.T. (2001) Computational methods for the study of energies of cation distributions: applications to cation-ordering phase transitions and solid solutions. Mineralogical Magazine, 65, 197–224.Google Scholar
Botella, V., Timón, V., Hernández-Laguna, A. & Sainz-Díaz, C.I. (2004) Hydrogen bonding and vibrational properties of hydroxy groups in the crystal lattice of dioctahedral clay minerals by means of First Principles calculations. Physics and Chemistry of Minerals, 31, 475–486.CrossRefGoogle Scholar
Cuadros, J., Sainz-Díaz, C.I., Ramirez, R. & Hernández-Laguna, A. (1999) Analysis of Fe segregation in the octahedral sheet of bentonitic illite-smeetite by means of FT-IR, 27A1 MAS NMR and reverse Monte Carlo simulations. American Journal of Science, 299, 289–308.CrossRefGoogle Scholar
Escamilla-Roa, E. (2005) Investigatión mecano-cuántica de las estructuras cristalinas, propiedades espectroseópicas y reactividad de filosilicatos 2:1 dioctaédricos. PhD Thesis. Universidad de Granada, Spain.Google Scholar
Filiaps, C.I., Huo, D., Yan, L., Wu, J. & Stucki, J.W. (2002) Infrared study of reduced and reduced-reoxidized ferruginous smectite. Clays and Clay Minerals, 50, 455–469.Google Scholar
Hernández-Laguna, A., Escamilla-Roa, E., Timón, V., Dove, M.T. & 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, 655–666.Google Scholar
Herrero, C.P. & Sanz, J. (1991) Short-range order of the Si, Al distribution in layer silicates. Journal of Physics and Chemistry of Solids, 52, 1129–1135.Google Scholar
Hobbs, J.D., Cygan, R.T., Nagy, K.L., Schultz, P.A. & Sears, M.P. (1997) All-atom ab initio energy minimization of the kaolinite crystal structure. American Mineralogist, 82, 657–662.CrossRefGoogle Scholar
Lee, J.H. & Guggenheim, S. (1981) Single crystal X-ray refinement of pyrophyllite-. Tc. American Mineralogist, 66, 350–357.Google Scholar
Louie, S.G., Froyen, S. & Cohen, M.L. (1982) Nonlinear ionic pseudopotentials in spin-density-functional calculations. Physics Review, B26, 1738–1742.Google Scholar
Meunier, A. (2006) Why are clay minerals small. Clay Minerals, 41, 551–566.CrossRefGoogle Scholar
Palin, E.J., Dove, M.T., Redfern, S.A.T., Bosenick, A., Sainz-Díaz, C.I. & Warren, M.C. (2001) Computational study of tetrahedral Al-Si ordering in muscovite. Physics and Chemistry of Minerals, 28, 534–544.CrossRefGoogle Scholar
Pelletier, M., Michot, L.J., Humbert, B., Barres, O., D'Espinose de la Caillerie, J.-B. & Robert, J.-L. (2003) Influence of layer charge on the hydroxyl stretching of trioctahedral clay minerals: A vibrational study of synthetic Na- and K-saponites. American Mineralogist, 88, 1801–1808.CrossRefGoogle Scholar
Perdew, J.P., Burke, K. & Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 77, 3865–3868.Google Scholar
Sainz-Díaz, C.I., Cuadros, J. & Hernández-Laguna, A. (2001a) Analysis of cation distribution in the octahedral sheet of dioctahedral 2:1 phyllosilicates by using inverse Monte Carlo methods. Physics and Chemistry of Minerals, 28, 445–454.Google Scholar
Sainz-Díaz, C.I., Hernández-Laguna, A. & Dove, M.T. (2001b) Modelling of dioctahedral 2:1 phyllosilicates by means of transferable empirical potentials. Physics and Chemistry of Minerals, 28, 130–141.Google Scholar
Sainz-Díaz, C.I., Timón, V., Botella, V., Artacho, E. & Hernández-Laguna, A. (2002) Quantum mechanical calculations of dioctahedral 2:1 phyllosilicates: Effect of octahedral cation distribution in pyrophyllite, illite and smectite. American Mineralogist, 87, 958–965.CrossRefGoogle Scholar
Sainz-Díaz, C.I., Escamilla-Roa, E. & Hernández-Laguna, A. (2005) Quantum mechanical calculations of transvacant and cis-vacant polymorphism in dioctahedral 2:1 phyllosilicates. American Mineralogist, 90, 1827–1834.Google Scholar
Saáchez-Portal, D., Ordejón, P., Artacho, E. & Soler, J.M. (1997) Density-functional method for very large systems with LCAO basis sets. International Journal of Quantum Chemistry, 65, 453–461.Google Scholar
Soler, J.M., Artacho, E., Gale, J.D., García, A., Junquera, J., Ordejón, P. & Saáchez-Portal, D. (2002) The SIESTA method for ab initio order-N materials simulation. Journal of Physics Condensed Matter, 14, 2745–2779.Google Scholar
Stixrude, L. & Peacor, D.R. (2002) First-principles study of illite-smeetite and implications for clay mineral systems. Nature, 420, 165–168.CrossRefGoogle ScholarPubMed
Tsipursky, S.I. & Drits, V.A. (1984) The distribution of octahedral cations in the 2:1 layers of dioctahedral smectites studied by oblique-texture electron diffraction. Clay Minerals, 19, 177–193.Google Scholar
Troullier, N. & Martins, J.L. (1991) Efficient pseudopotentials in spin-density-functional calculations. Physics Review, B43, 1993–2006.Google Scholar
Vantelon, D., Montarges-Pelletier, E., Michot, L.J., Briois, V., Pelletier, M. & Thomas, F. (2003) Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study. Physics and Chemistry of Minerals, 30, 44–53.Google Scholar
Wardle, R. & Brindley, G.W. (1972) The crystal structures of pyrophyllite-1 Tc, and its dehydroxylate. American Mineralogist, 57, 732–750.Google Scholar