Spin Density Distribution in Transition Metal Complexes: Some Thoughts and Hints

Abstract

The spin density distribution in transition metal complexes is discussed in qualitative terms, taking into account the coexistence of spin delocalization and spin polarization mechanisms, with the help of numerical results for several complexes obtained from density functional calculations. The covalent character of the metal-ligand bonds as well as the σ- or π-characteristics of the partially filled d orbitals must be taken into account to qualitatively predict the sign of the spin density at a particular atom within a ligand. The same patterns can be applied to binuclear complexes and can be helpful in determining the ferro- or antiferromagnetic character of the exchange coupling between two paramagnetic ions when the energy gap between the partially occupied molecular orbitals is small. An attempt is made to establish a link between the qualitative-Hay-Thibeault-Hoffmann model of exchange coupling and the of spin polarization model.