Influence of madelung (interatomic Coulomb) energy on Wolfsberg–Helmholz calculations

Abstract

AbstractA model is presented for the estimation of ionicities in molecules and complex ions. The model uses the minimization of total energy by the method of differential ionization energies. The effect of Madelung corrections to the energies is considered, and the model is refined by evaluating the covalent‐bond energies.Wolfsberg–Helmholz calculations have been applied to the same type of model, also incorporating Madelung corrections. The Madelung corrections make the metal ionization energy curves less steep, and the ligand ionization energies are nearly invariant with charge. This creates a situation which has previously been artificially imposed by selecting the ligand ionization energies to give desirable terms in the Wolfsberg–Helmholz secular determinant. The effect of Madelung energy is shown to be the primary influence in describing the ionicity and total energy of a chromophore; covalent bonding effects are shown to be secondary when the ligands and the central atom have fairly different electronegativities.