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An alternative approach to non-molecular crystal structures with emphasis on the arrangements of cations

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Cation Ordering and Electron Transfer

Part of the book series: Structure and Bonding ((STRUCTURE,volume 61))

Abstract

The alternative approach to structures is an inversion of the traditional one: we concentrate on a packed array of cations, into the interstices of which the anions are inserted, rather than putting cations into a packed anion array. Even in conventional terms the logic of the new approach can be justified, since many structures have their own antitypes (and even more show a partial structure/antistructure relation).

In this way we find that, in oxides for example, many cation arrangements are identical to the arrangements of the atoms in known (or plausible) alloy structures. (In some cases the cations and atoms are identical in the two cases.) This is particularly helpful in those oxide examples where it has not previously been possible to describe the structure in any simple terms, often because the anion array is not regular in any simple way, for instance in many metal sulphates. But it is also revealing in some cases that are describable in conventional terms, e.g. the humites. A long (but still incomplete) list of examples is given in Table 3. Sufficient specific cases are described and discussed in detail in the text in order to expose the principles and some of the advantages of this unfamiliar approach.

One of these advantages is that, in favourable cases, it leads at once to complete quantitative descriptions of the structures (i.e. until cell dimensions and anion position parameters), e.g. for spinel, garnet, bixbyite etc. Another is that it throws a new light on possible martensitic mechanisms for phase transformations (e.g. β- → γ-Ca2SiO4, low- → high-temperature K2SO4), and on the possibility of anomalous substitution (e.g. of CO 2−3 for PO 3−4 in apatite). It also reveals an explanation for those phase transitions, due to high pressure, that are not attended by an increase in primary coordination number, e.g. olivine → spinel, zircon → scheelite.

The important thing in science is not so much to obtain new facts as to discover new ways of thinking about them. W. L. Bragg105)

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Authors and Affiliations

  1. Department of Chemistry, Arizona State University, Tempe, Arizona, U.S.A.

    M. O’Keeffe

  2. Research School of Chemistry, Australian National University, Canberra, A.C.T., Australia

    B. G. Hyde

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  1. M. O’Keeffe
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  2. B. G. Hyde
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O’Keeffe, M., Hyde, B.G. (1985). An alternative approach to non-molecular crystal structures with emphasis on the arrangements of cations. In: Cation Ordering and Electron Transfer. Structure and Bonding, vol 61. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0111193

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  • DOI: https://doi.org/10.1007/BFb0111193

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  • Online ISBN: 978-3-540-39430-3

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