Direct theoretical abinitio calculations in exchange coupled copper (II) dimers: Influence of structural and chemical parameters in modeled copper dimers

The influence of structural and chemical parameters on the singlet–triplet splitting (2J=ΔEST ) in modeled exchange coupled oxygen‐bridged dimeric copper (II) complexes is studied, using an ab initio method followed by a perturbation development of the configuration interaction. The effect of varying the Cu–O–Cu′ angle and the Cu–O distance in the Cu2O2 core of modeled dimers is calculated. The results are comparable to the experimental ones. Changes in the geometric coordination around the copper (II) atom and around the oxygen atom of the core are studied. The results show that the magnitude of the exchange coupling strongly depends on both of these factors. Electronegativity effects are studied by varying the counterion in the model and by changing from alkoxo‐bridged to hydroxo‐bridged copper (II) dimers.

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