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 ͑LMCT͒ 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 et al., J. Chem. Phys. 116, 2728 ͑2002͔͒ 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 ferroand antiferromagnetic contributions to the coupling constant.

The performance of multiconfigurational second-order perturbation techniques is established for the calculation of small magnetic couplings in heterobinuclear complexes. Whereas CASPT2 gives satisfactory results for relatively strong magnetic couplings, the method shows important deviations from the expected Heisenberg spectrum for couplings smaller than 15-20 cm(-1). The standard choice of the zeroth-order CASPT2 Hamiltonian is compared to alternative definitions published in the literature and the stability of the results is tested against increasing level shifts. Furthermore, we compare CASPT2 with an alternative implementation of multiconfigurational perturbation theory, namely NEVPT2 and with variational calculations based on the difference dedicated CI technique.

The N2+ molecule is studied at different interatomic distances as a model molecule for the double exchange mechanism. The energy spectrum as well as the wave functions of the lowest states are analyzed and confronted both with the usual model of double exchange and with a recently proposed refined model. It is shown that the usual model fails to reproduce the energy spacings while the refined model is valid on a large domain of interatomic distances (in the magnetic regime). The study of a model molecule on a large domain of interatomic distances makes it possible to systematically investigate several regimes associated with different energetic state orderings. The perfect agreement between the refined model and the computed energies in the whole domain of stretched distances shows its applicability to a large number of real compounds. Finally, the respective contributions of dynamical and nondynamical correlations are analyzed.

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