Abstract
THE structure and stability of an inorganic solid is determined in general both by short-range covalent and by long-range electrostatic forces. Here we describe the use of interatomic force fields developed recently from first-principles quantum-chemical cluster calculations1,2 in the study of the structures of SiO2 tetrahedral networks. We find that the symmetry of these structures depends sensitively on the balance between ionic and covalent forces: high-symmetry structures are stabilized for relatively large ion partial charges, and low-symmetry structures are stabilized when the ionicity is small. For some SiO2 polymorphs, the low-symmetry structures found in our simulations correspond to the low-temperature phases of these polymorphs found experimentally. A reinterpretation of structural data on quartz provides evidence for temperature dependence of the ionicity, which can explain the change of symmetry observed when temperature is increased. Our preliminary calculations on aluminophosphates suggest that this symmetry-breaking mechanism may also provide insight into the structural changes observed for complex molecular sieves.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Van Beest, B. W. H., Kramer, G. J. & Van Santen, R. A. Phys. Rev. Lett. 64, 1955–1958 (1990).
Kramer, G. J., Farragher, N. P., Van Beest, B. W. H. & Van Santen, R. A. Phys. Rev. B43, 5068–5080 (1991).
Dovesi, R., Pisani, C. Roetti, C. & Silvi, B. J. chem. Phys. 86, 6967–6971 (1987).
Allan, D. C. & Teter, M. P. Phys. Rev. Lett. 59, 1136–1139 (1987).
Catlow, R. C. A. & Price, G. D. Nature 347, 243–248 (1990).
Lasaga, A. C. & Gibbs, G. V. Phys. Chem. Miner. 14, 107–117 (1987).
Tsuneyuki, S., Tsukada, M., Aoki, H. & Matsui, Y. Phys. Rev. Lett. 61, 869–872 (1988).
Tsuneyuki, S., Matsui, Y., Aoki, H. & Tsukada, M. Nature 339, 209–211 (1989).
Nye, J. F. Physical Properties of Crystals (Oxford University Press, Oxford, 1957).
Meier, W. M. & Olson, D. H. Atlas of Zeolite Structure Types, 2nd edn (Butterworth, Cambridge, 1987).
Axe, J. D. & Shirane, G. Phys. Rev. B1, 342–348 (1970).
Peacor, D. R. Z. Kristallogr. 138, 274–298 (1973).
Fyfe, C. A., Strobl, H., Kokotailo, G. T., Kennedy, G. J. & Barlow, G. E. J. Am. chem. Soc. 110, 3373–3380 (1988).
Grimm, H. & Dorner, B. J. Phys. Chem. Solids 36, 407–413 (1975).
Van Santen, R. A. & Vogel, D. L. Adv. Solid St. Chem. 1, 151–224 (1989).
Lasaga, A. C. & Gibbs, G. V. Phys. Chem. Miner. 16, 29–41 (1988).
Tsuneyuki, S., Aoki, H., Tsukada, M. & Matsui, Y. Phys. Rev. Lett. 64, 776–779 (1990).
Gouhara, K. & Kato, N. J. phys. Soc. Japan 54, 1868–1881; 1882–1889 (1985).
Mukamel, D. & Walker, M. B. Phys. Rev. Lett. 58, 2559–2562 (1987).
Phillips, J. C. Bonds and Bands in Semiconductors (Academic, New York, 1973).
Dessau, R. M., Schlenker, J. L. & Higgins, J. B. Zeolites 10, 522–524 (1990).
Rudolf, P. R. & Crowder, C. E. Zeolites 10, 163–168 (1990).
McCusker, L. B., Baerlocher, C., Jahn, E. & Bülow, M. Zeolites (in the press).
Davis, M. E., Saldarriaga, C., Montes, C., Garces, J. & Crowder, C. Zeolites 8, 362–366 (1988).
Tezuka, Y., Shin, S. & Ishigame, M. Phys. Rev. Lett. 66, 2356 (1991).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kramer, G., van Beest, B. & van Santen, R. Relation between crystal symmetry and ionicity in silica polymorphs. Nature 351, 636–638 (1991). https://doi.org/10.1038/351636a0
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/351636a0
This article is cited by
-
Framework silica structures generated using simulated annealing with a potential energy function based on an H6Si2O7 molecule
Physics and Chemistry of Minerals (1994)
-
Ionicity in silica
Nature (1991)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.