Structural relationships between cations and alloys; an equivalence between oxidation and pressure

Abstract

More than 100 examples are provided of the structural identity between the cation arrays in oxides and their corresponding alloys (binary compounds). Halides and halogenates, sulfides and sulfites and/or sulfates, selenides and selenates, phosphides and phosphates show this behaviour. In some cases, the structure of the cation subarray corresponds to the structure of the alloy at ambient conditions, but in other cases, cations stabilize structures which correspond to those of the high-pressure phases of the alloy, from which an analogy between the insertion of oxygen and the application of pressure can be established. In this last case, the oxides show polymorphism with temperature and when heated, the structure of the ambient pressure of the alloy is recovered as if heating would compensate the effect of pressure. From the results reported here, it is concluded that cations do not seem to be either the isolated entities, predicted by the ionic model, which occupy interstices of an oxygen matrix, or they arrange in a more or less arbitrary way, but they try to reproduce the structure of their corresponding alloy. Many of the phase transitions and the polymorphism exhibited by the oxides described here are better explained when they are considered as formed by previous entities which are the alloys. Oxides should be considered as `real stuffed alloys'. These features do not seem to be casual, but they obey a general principle: Cations recognize themselves in spite of being embedded in an oxygen bulk. The nature and the physical meaning of this recognition are problems which remain unsolved.