Skip to main content Accessibility help
×
Home

Quantum mechanical study of Al/Si disorder in leucite and bicchulite

  • B. Winkler (a1), V. Milman (a2) and C. J. Pickard (a3)

Abstract

We have studied the structures of Al/Si disordered leucite and bicchulite with a quantum mechanical version of the virtual crystal approximation, VCA. In leucite, the average tetrahedron has a composition of (AlSi2)O4, while bicchulite represents an extreme case with (Al2Si)O4 tetrahedra. Both structures are well described with the VCA. In conjunction with an earlier study, where we have shown that the (AlSi)O4 tetrahedra in gehlenite and Al,Si-disordered octahedra are also well reproduced, we have now established that the VCA gives a reliable description of the averaged structure of disordered aluminosilicates over the whole compositional range. The current calculations confirm that Al/Si ordering is not driving the cubic to tetragonal phase transformation in leucite. In bicchulite, the model calculations are consistent with hydrogen on Wyckoff position 8c, in agreement with the result of a single crystal X-ray diffraction study, but in variance with results based on a neutron powder diffraction study.

Copyright

Corresponding author

References

Hide All
Bachelet, G.B., Hamann, D.R. and Schlüter, M. (1982) Pseudopotentials that work: from H to Pu. Physical Review, B26, 41994228.
Bellaiche, L. and Vanderbilt, D. (2000) Virtual crystal approximation revisited: Application to dielectric and piezoelectric properties of perovskites. Physical Review B, 61, 78777882.
Dann, S.E., Mead, P.J. and Weller, M.T. (1996) Löwenstein's rule extended to an aluminium rich framework. The structure of bicchulite, Ca8(Al2SiO6)4(OH)8, by MASNMR and neutron diffraction. Inorganic Chemistry, 35, 14271428.
de Gironcoli, S., Giannozzi, P. and Baroni, S. (1991) Structure and thermodynamics of Si x Ge1–x alloys from ab initio Monte Carlo simulations. Physical Review Letters, 66, 21162119.
Depmeier, W. (1984) Tetragonal tetrahedra distortions in cubic sodalite frameworks. Acta Crystallographica, B40, 185191.
Dove, M.T., Cool, T., Palmer, D.C., Putnis, A., Salje, E.K.H. and Winkler, B. (1993) On the role of Al-Si ordering in the cubic-tetragonal phase transition in leucite. American Mineralogist, 78, 486492.
George, A.M., Iniguez, J. and Bellaiche, L. (2001) Anomalous properties in ferroelectrics induced by atomic ordering. Nature, 413, 5457.
Goniakowski, J., Holender, J.M., Kantorovich, L.N., Gillan, M.J. and White, J.A. (1996) Influence of gradient corrections on the bulk and surface properties of TiO2 and SnO2 . Physical Review B, 53, 957960.
Hamann, D.R. (1996) Generalized gradient theory for silica phase transitions. Physical Review Letters, 76, 660663.
Hammer, B., Jacobsen, K.W. and Norskov, J.K. (1993) Role of non local exchange-correlation in activated adsorption. Physical Review Letters, 70, 39713974.
Hohenberg, P. and Kohn, W. (1964) Inhomogeneous electron gas. Physical Review, 136, B864B871.
Iniguez, J. and Bellaiche, L. (2001) Ab Initio design of perovskite alloys with predetermined properties: The case of Pb(Sc0.5Nb0.5)O3 . Physical Review Letters, 87, 095503-1-095503-4.
Jones, R.O. and Gunnarsson, O. (1989) The density functional formalism, its applications and prospects. Reviews of Modern Physics, 61, 689746.
Kleinman, L. and Bylander, D.M. (1982) Efficacious form for model pseudopotentials. Physical Review Letters, 48, 14251428.
Kohn, W. and Sham, L.J. (1965) Self-consistent equations including exchange and correlation effects. Physical Review, 140, A1133A1138.
Kresse, G. and Hafner, J. (1994) Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements. Journal of Physics: Condensed Matter, 6, 82458257.
Kryachko, E.S. and Ludena, E.V. (1990) Energy Density Functional Theory of many-electron Systems. Understanding Chemical Reactivity, vol. 4. Kluwer Academic Publishers, Dordrecht, The Netherlands.
Leung, T.C., Chan, C.T. and Harmon, B.N. (1991) Ground-state properties of Fe, Co, Ni and their monoxides: results of the generalized gradient approximation. Physical Review B, 44, 29232927.
Marzari, N., de Gironcoli, S. and Baroni, S. (1994) Structure and phase stability of Ga x In1–x P solid solutions from computational alchemy. Physical Review Letters, 72, 40014004.
Milman, V., Winkler, B., White, J.A., Pickard, C.J., Payne, M.C., Akhmatskaya, E.V. and Nobes, R.H. (2000) Electronic structure, properties, and phase stabilities of inorganic crystals: a pseudopotential plane-wave study. International Journal of Quantum Chemistry, 77, 895910.
Monkhorst, H.J. and Pack, J.D. (1976) Special points for Brillouin-zone integration. Physical Review B, 13, 51885192.
Myers, E.R., Heine, V. and Dove, M.T. (1998) Thermodynamics of Al/Al avoidance in the ordering of Al/Si tetrahedral framework structures. Physics and Chemistry of Minerals, 25, 457464.
Palmer, D.C., Salje, E.K.H. and Schmahl, W.W. (1989) Phase transitions in leucite: X-ray diffraction studies. Physics and Chemistry of Minerals, 16, 714719.
Parr, R.G. and Yang, W. (1989) Density-functional Theory of Atoms and Molecules. Oxford University Press, Oxford, UK.
Pauling, L. (1930) The structure of sodalite and helvite. Zeitschrift für Kristallographie, 74, 213225.
Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized Gradient approximation made simple. Physical Review Letters, 77, 38653868.
Ramer, N.J. and Rappe, A.M. (2000) Virtual crystal approximation that works: locating a compositional phase boundary in Pb(Zr1-x Ti x )O3 . Physical Review B, 62, R743R746.
Sahl, K. (1980) Refinement of the crystal structure of bicchulite, Ca2(Al2SiO6)(OH)2 . Zeitschrift für Kristallographie, 152, 1321.
Segall, M.D., Lindan, P.J.D., Probert, M.J., Pickard, C.J., Hasnip, P.J., Clark, S.J. and Payne, M.C. (2002) First-principles simulation: ideas, illustrations and the CASTEP code. Journal of Physics: Condensed Matter, 14, 27172744.
Soven, P. (1967) Coherent-potential model of substitutional disordered alloys. Physical Review, 156, 809813.
Taylor, D. and Henderson, C.M.B. (1978) A computer model for the cubic sodalite structure. Physics and Chemistry of Minerals, 2, 325336.
Thayaparam, S., Dove, M.T. and Heine, V. (1994) A computer simulation study of Al/Si ordering in gehlenite and the paradox of the low transition temperature. Physics and Chemistry of Minerals, 21, 110116.
Vanderbilt, D. (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Physical Review, B41, 78927895.
Winkler, B., Dove, M.T. and Leslie, M. (1991) Static lattice energy minimization and lattice dynamics calculations on aluminosilicate minerals. American Mineralogist, 76, 313331.
Winkler, B., Pickard, C. and Milman, V. (2002) Applicability of a quantum mechanical ‘virtual crystal approximation’ to study Al/Si-disorder. Chemical Physics Letters, 362, 266270.

Keywords

Related content

Powered by UNSILO

Quantum mechanical study of Al/Si disorder in leucite and bicchulite

  • B. Winkler (a1), V. Milman (a2) and C. J. Pickard (a3)

Metrics

Altmetric attention score

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.