title: Mimicking the two-dimensional spectrochemical series using density functional computations.
abstract: 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 sigma and pi 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.
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Denmark.
authors.forename: Christian
authors.initials: C
authors.lastname: Anthon
authors.forename: Jesper
authors.initials: J
authors.lastname: Bendix
authors.forename: Claus E
authors.initials: CE
authors.lastname: Schäffer