Development of parameter sets for semi-empirical MO calculations of transition metal systems: iron parameters for iron-sulfur proteins.

A semi-empirical parameter set for iron has been developed which is appropriate for the study of iron-sulfur proteins having a single iron atom, by fitting to density-functional theory (DFT) calculations obtained for a series of small models of iron-containing proteins. These parameters are obtained using a modified BFGS optimisation procedure previously used to obtain semi-empirical parameters for the main group elements. The modifications to this procedure for obtaining parameters for transition metal atoms are outlined. In addition to modifications to the semi-empirical core repulsion function, which yield significant improvements in the calculation of molecular structures, compared to the standard core repulsion function, are outlined. The reported parameters are then tested on a set of model complexes containing a variety of ligands and show good agreement with both DFT and experimental data for these species.