Ab Initio and Coupled-Perturbed Density Functional Theory Estimation of Zero-Field Splittings in Mn^II Transition Metal Complexes

The paper presents a method comparison for the prediction of zero-field splitting (ZFS) parameters in a series of MnII coordination complexes. The test set consists of MnII complexes that are experimentally well-characterized by X-ray diffraction and high-field electron paramagnetic resonance. Their ZFS parameters have been calculated using density functional theory (DFT) as well as complete active space self-consistent field (CASSCF) methods. It is shown that the recently introduced coupled-perturbed spin−orbit coupling (CP-SOC) approach [Neese, F. J. Chem. Phys. 2007, 127, 164112] together with hybrid-DFT functionals leads to a slope of the correlation line (plot of experimental vs calculated D values) that is essentially unity provided that the direct spin−spin interaction is properly included in the treatment. This is different from our previous DFT study on the same series of complexes where a severe overestimation of the D parameter has been found [Zein, S., Duboc, C., Lubitz, W., and Neese, F. Inorg. Chem. 2008, 47, 134]. CASSCF methods have been used to evaluate the ZFS in an "ab initio ligand-field" type treatment. The study demonstrates that a substantial part of the relevant physics is lost in such a treatment since only excitations within the manganese d-manifold are accounted for. Thus, a severe underestimation of the D parameter has been found. Because the CASSCF calculations in combination with quasidegenerate perturbation theory treats the SOC to all orders, we have nevertheless verified that second-order perturbation theory is an adequate approximation in the case of the high-spin d5 configuration.