A new theory of compressible ions - structures of the alkali halides

Abstract

Ions in ionic crystals are considered to exist in compressible space-filling polyhedral cells analogous to the Wigner-Seitz cell in metals. Repulsion arises from the compression energy of the ions written as a surface integral over the ionic cells. Two adjustable parameters are introduced per ion with the provision that the same parameters can be used in any crystal of any structure in which the ion occurs. The 18 parameters for the 5 alkali and 4 halogen ions have been determined from PV data on the 20 alkali halides. The important successes of the theory are: (i) All the twenty alkali halides are correctly predicted to occur in their observed structures (ii) The thermal transition in CsCl is explained (iii) The pressure transitions in the alkali halides are predicted well (iv) The calculated values of the variation of transition pressures with temperature agree well with experiment. These results are much better than those obtained by earlier theories.