Ligand field spectroscopy and chemical bonding in Cr 3+-, Fe 3+-, Co 2+- and Ni 2+-containing oxidic solids : Influence of the inductive effect of the competing bonds and magnetic interactions on the degree of covalency of the 3d M–O bonds

Abstract

The correlations between B 35 and the ionic-covalent parameter ICP nn for various 3d n electronic configurations (3d 3, 3d 5, 3d 7, 3d 8) in mixed oxides reveal the effect of the nearest cationic shell on bonding in the transition metal coordination polyhedron. The variations of B 35 with the optical basicity calculated from the valence and coordination numbers of the component cations show that the physical interpretation of the Racah parameter in terms of so-called covalency effects should be viewed with some caution. A much closer correlation between the Racah parameters and the degree of covalency of M–O bonds is achieved when the inductive effect and the influence of magnetic interactions are taken into account.