Evaluation of magnetic terms in Cu4O4 cubane-like systems from selected configuration interaction calculations: A case study of polynuclear transition-metal systems

We present the evaluation of magnetic terms in a Cu4O4 cubane-like system from truncated CI calculations, as a case study of polynuclear transition-metal complexes. We employ a new excitation selected configuration interaction (EXSCI) method based on the use of local orbitals. Taking advantage of the locality and then of the fact that the interactions vanish when the distance is large, the dimension of the CI is largely reduced. To the best of our knowledge these CI calculations are the largest one performed for polynuclear transition metal systems so far. The results show the presence of two leading ferromagnetic interactions between bridged Cu ions. Also the interactions between the unbridged Cu ions are ferromagnetic, but very weak, in contrast to the experimental data. The nature and amplitude of all the computed interactions are consistent with the relative orientation of the magnetic orbitals in the molecule, and correctly reproduce the susceptibility versus temperature curve. Our results indicate that it is possible to obtain similar fittings with sets of parameters representing different physical effects and put in evidence the drawbacks of the fitting based on oversimplified magnetic models. In this context, the presented computational strategy can be considered as a useful tool to help in the interpretation of the magnetic data and the validation of the magnetic interaction model in the polynuclear magnetic systems.