25: Inorganic and Mineral Structures Reconsidered (1986)
Abstract
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."
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