Analysis of the magnetic coupling in binuclear systems. III. The role of the ligand to metal charge transfer excitations revisited

In magnetic coordination compounds and solids the magnetic orbitals are essentially located on metallic centers but present some delocalization tails on adjacent ligands. Mean field variational calculations optimize this mixing and validate a single band modelization of the intersite magnetic exchange. In this approach, due to the Brillouin's theorem, the ligand to metal charge transfer (LMCT) excitations play a minor role. On the other hand the extensive configuration interaction calculations show that the determinants obtained by a single excitation on the top of the LMCT configurations bring an important antiferromagnetic contribution to the magnetic coupling. Perturbative and truncated variational calculations show that contrary to the interpretation given in a previous article [C. J. Calzado , J. Chem. Phys. 116, 2728 (2002)] the contribution of these determinants to the magnetic coupling constant is not a second-order one. An analytic development enables one to establish that they contribute at higher order as a correlation induced increase in the LMCT components of the wave function, i.e., of the mixing between the ligand and the magnetic orbitals. This larger delocalization of the magnetic orbitals results in an increase in both the ferro- and antiferromagnetic contributions to the coupling constant.