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Mimicking the Two-Dimensional Spectrochemical Series Using Density Functional Computations

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journal contribution
posted on 29.11.2004, 00:00 by Christian Anthon, Jesper Bendix, Claus E. Schäffer
With tetragonal distortions of tetrahedral d2 complexes as examples, nonadditive and additive ligand fields are compared computationally, using Kohn−Sham density functional theory (KS−DFT) and ligand-field theory to obtain 45 linear, parametrical equations. For each complex, a “data” reduction from three nonadditive-field parameters to two parameters of the additive field occurs. The complexes V and CrX4 (where X = F, Cl, Br, I) provide the two-dimensional spectrochemical series of the σ and π AOM parameters, which are known semiempirically for the halide ligands. The same parametrical results can be obtained from the Kohn−Sham orbital energies of the “average of configuration” computation.