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Abstract:
This work presents a detailed evaluation of the performance of density functional theory (DFT) for the prediction of zero-field splittings (ZFSs) in Mn(II) coordination complexes. Eighteen experimentally well characterized four-, five-, and six-coordinate complexes of the general formula [Mn(L)nL‘2] with L‘ = Cl, Br, I, NCS, or N3 (L = an oligodentate ligand) are considered. Several DFT-based approaches for the prediction of the ZFSs are compared. For the estimation of the spin−orbit coupling (SOC) part of the ZFS, it was found that the Pederson−Khanna (PK) approach is more successful than the previously proposed quasi-restricted orbitals (QRO)-based method. In either case, accounting for the spin−spin (SS) interaction either with or without the inclusion of the spin-polarization effects improves the results. This argues for the physical necessity of accounting for this important contribution to the ZFS. On average, the SS contribution represents ∼30% of the axial D parameters. In addition to the SS part, the SOC contributions of d−d spin flip (αβ) and ligand-to-metal charge transfer excited states (ββ) were found to dominate the SOC part of the D parameter; the observed near cancellation between the αα and βα parts is discussed in the framework of the PK model. The calculations systematically (correlation coefficient ∼0.99) overestimate the experimental D values by ∼60%. Comparison of the signs of calculated and measured D values shows that the signs of the calculated axial ZFS parameters are unreliable once E/D > 0.2. Finally, we find that the calculated D and E/D values are highly sensitive to small structural changes. It is observed that the use of theoretically optimized geometries leads to a significant deterioration of the theoretical predictions relative to the experimental geometries derived from X-ray diffraction. The standard deviation of the theoretical predictions for the D values almost doubles from ∼0.1 to ∼0.2 cm-1 upon using quantum chemically optimized structures. We do not find any noticeable improvement in considering basis sets larger than standard double- (SVP) or triple-ζ (TZVP) basis sets or using functionals other than the BP functional.
