DETERMINATION OF THE BONDING AND VALENCE DISTRIBUTION IN INORGANIC SOLIDS BY THE MAXIMUM-ENTROPY METHOD

The distribution of valence among the bonds in the bond graph of an in organic compound is used to calculate an 'entropy'. We show that the d istribution of valence that maximizes this entropy (ME) is similar, bu t not identical, to that obtained using the equal-valence rule (EVR) p roposed by Brown [Acta Cryst. (1977), B33, 1305-1310]. Since the ME so lutions are maximally non-committal with regard to missing information , they give better predictions of the observed valence distributions t han the EVR solutions when lattice constraints or electronic anisotrop ies are present, but worse predictions when these effects are absent. Since valences calculated using ME are necessarily positive, they give significantly better predictions in cases where EVR predicts a negati ve bond valence. In the absence of electronic distortions the observed bond graph is either the graph with the highest maximum entropy or it has an entropy within 1% of this value. Since the entropy depends on the oxidation states of the atoms, compounds with the same stoichiomet ry and cation coordination numbers but different atomic valences may a dopt different bond graphs and hence different structures.