25: Inorganic and Mineral Structures Reconsidered (1986)
Liversidge Research Lecture delivered before the Royal Society of New South Wales, September 24th, 1986, at The University of Sydney. Reproduced by permission of the Royal Society of New South Wales from J. Proc. Roy. Soc. N.S.W., 1986, 119, 153-164.
"For 60 years or so the "Ionic Model" has been fundamental to solid state chemistry and mineralogy. It has been useful, but the ideas involved have become sacrosanct, even when they do not work! Quantum mechanical methods are becoming increasingly important and useful, but they lack the simple "physical" approach and, in any case, so far can only be applied to the simpler structures."
"An alternative approach, as simple, naive and "physical" as the ionic model, is successful where the latter succeeds and where it fails (e.g. in silicates). It can often be useful for simple and complicated structures; and it avoids the ionic/covalent dichotomy. Like the successful quantum methods, it sees no difference in principle between non-molecular structures and those of small molecules (another unhappy dichotomy). It emphasises that, as in organic chemistry, one "size" for an atom is insufficient for understanding structure; at the crudest level one needs a bonding size (for first nearest neighbour interactions) and a non-bonding size (for second and further neighbours)."
"It transpires that cations, far from being small in size and influence, often dominate crystal structure and behaviour."
Barlow, W., 1898. Geometrische Untersuchung Uber eine mechanische Ursache der Homogenität der Structur und der Symmetrie; mit besonderer Anwendung auf Krystallisation und chemische Verbindung. Z. Kristallogr., 29, 433-588.
Bärnighausen, H., Bossert, W. and Anselment, B., 1984. A second-order phase transition of calcium bromide and its geometrical interpretation. Acta Cryst., A40 suppl., C-96.
Bartell, L.S. , 1968. Molecular geometry: bonded versus non-bonded interactions. J. Chem. Ed., 45, 754-767.
Bragg, L. and Claringbull, G.F., 1965. The Crystal Structures of Minerals. Bell, London., p.232.
Brown, I.D. and Altermatt, D., 1985. Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database. Acta Cryst., B41, 244-247.
Brunner, G.O., 1971. An unconventional view of the 'closest sphere packings'. Acta Cryst., A27, 388-390.
Bukowinski, M.S.T., 1982. Pressure effects on bonding in CaO: comparison with MgO. J. Geophys. Res., 87, 303-310.
Burdett, J. K. and Caneva, D., 1985. The energetic description of solids in terms of small fragments. Inorg. Chem., 24, 3866-3873.
Clementi, E. and Roetti, C., 1974. Roothaan-Hartree-Fock atomic wavefunctions. Basis functions and their coefficients for ground and certain excited states of neutral and ionised atoms, Z ≤ 54. Atomic Data and Nuclear Data Tables, 14, 177-478.
Fischer, R. and Zemann, J., 1975. Geometrische und elektrostatische Berechnungen am Quarz- und am Cristobalit-Type. I. Modelle mit AB4-Tetraedern der Symmetrie 43m. TMPM Tschermaks Min. Petr. Mitt., 22, 1-14.
Fumi, F.G. and Tosi, M.P., 1964. Ionic sizes and Born repulsive parameters in the NaCl-type alkali halides-I and II. J. Phys. Chem. Solids, 25, 31-43, 45-52.
Gibbs, G.V., 1982. Molecules as models for bonding in silicates. Amer. Mineral., 67, 421-450.
Hoppe, R. D., 1980. On the symbolic language of the chemist. Angew. Chem. Int. Ed. Eng., 19, 110-125.
Hyde, B.G., Sellar, J. R. and Stenberg, L., 1986. The β α' transition in Sr2SiO4 (and Ca2SiO4, K2SeO4, etc.), involving a modulated structure. Acta Cryst., B42, 423-429.
Kamb, B., 1968. Structural basis of the olivine-spinel stability relation. Amer. Mineral., 53, 1439-145S.
Kitaigorodsky, A.I., 1973. Molecular Crystals and Molecules. Academic Press, New York. Chapter VII.
McGuire, N. K. and O' Keeffe, M., 1984. Bond lengths in alkali metal oxides. J. Solid State Chem., 54, 49-53.
O'Keeffe, M., 1977. On the arrangements of ions in crystals. Acta Cryst. , A33, 924-927.
O'Keeffe, M. and Hyde, B.G., 1978. On Si-O-Si configurations in silicates. Acta Cryst., B34, 27-32.
O'Keeffe, M. and Hyde, B.G., 1981. The role of non-bonded forces in crystals, in M. O'Keeffe and A. Navrotsky (Eds.), Structure and Bonding in Crystals, Vol. 1, pp.227-254. Academic Press, New York.
O'Keeffe, M. and Hyde, B.G., 1984. Stoichiometry and the structure and stability of inorganic solids. Nature, 309, 411-414.
O'Keeffe, M. and Hyde, B.G., 1985. An alternative approach to non-molecular crystal structures, with emphasis on the arrangements of cations. Structure and Bonding (Berlin), 61, 77-144.
O'Keeffe, M. and Navrotsky, A. (Eds.), 1981. Structure and Bonding in Crystals. Vols. I and 2. Academic Press, New York.
O'Keeffe, M., Newton, M.D. and Gibbs, G.V., 1980. Ab initio calculation of interatomic force constants in H6Si2O7 and the bulk modulus of α-quartz and α-cristobalite. Phys. Chem. Miner., 6, 305-312.
Pauling, L., 1960. The Nature of the Chemical Bond. Cornell University Press, Ithaca, N.Y.
Shannon, R.D., 1976. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst., A32, 751- 767.
Stewart, R.F. and Spackman, M.,1981. Charge Density Distributions, in M. O'Keeffe and A. Navrotsky (Eds.), Structure and Bonding in Crystals, Vol. 1, p.296. Academic Press, New York.
Summerville, E.W., 1977. Private communication.
Wadsley, A.D., 1958. Modern structural inorganic chemistry. J. Proc. Roy. Soc. NSW, 92, 25-35.
Wyckoff, R.W.G. Crystal Structures, especially Vol. 4, Chapter XIII D, 2. Wiley, New York.