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Abstract:
An overview and a critical comparison of contemporary models to describe and to predict electronic multiplet structures and the spectroscopic behavior of transition-metal complexes with open d-shells is given in relation to experimental data including d-d absorption and ESR spectra. A ligand-field density-functional theory (LFDFT) predicts these properties with a success similar to ab initio approaches, such as the spectroscopy oriented configuration-interaction method, and better than time-dependent density-functional theory applied to open shell systems. Using well characterized systems, from classical coordination compounds [FeO4]2-, CrX63- (X=F,Cl), CoL6z(z=-3, L=CN-; z=2 and 3, L=H2O)] to FeIV macrocyclic compounds with biochemical and catalytic activity, it is shown that LFDFT is able also to characterize larger systems and subtle effects such as those from surrounding influences and the second coordination sphere.
