THE PRINCIPLES DETERMINING THE STRUCTURE OF COMPLEX IONIC CRYSTALS
J. Am. Chem. Soc., 1929, 51 (4), pp 1010–1026
DOI: 10.1021/ja01379a006
Publication Date: April 1929
1. The Relative Stability of Alternative Structures of Ionic Crystals.-
The elucidation of the factors determining the relative stability of alternative crystalline structures of a substance would be of the greatest significance in the development of the theory of the solid state. Why, for example, do some of the alkali halides crystallize with the sodium chloride structure and some with the cesium chloride structure? Why does titanium dioxide under different conditions assume the different structures of rutile, brookite and anatase? Why does aluminum fluosilicate, AlzSiOeF2, crystallize with the structure of topaz and not with some other structure? These questions are answered formally by the statement that in each case the structure with the minimum free energy is stable. This answer, however, is not satisfying; what is desired in our atomistic and quantum theoretical era is the explanation of this minimum free energy in terms of atoms or ions and their properties.
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