title: Computational studies of modified [Fe3S4] clusters: why iron is optimal.
abstract: This work reports density functional computations of metal-substituted models of biological [Fe3S4] clusters in oxidation states [MFe2S4](+/0/-1) (M=Mn, Fe, Co, Ni, Cu, Zn, and Mo). Geometry optimization with a dielectric screening model is shown to provide a substantial improvement in structure, compared to earlier used standard procedures. The error for average Fe-S bonds decreased from 0.038A to 0.016A with this procedure. Four density functionals were compared, B3LYP, BP86, TPSS, and TPSSh. B3LYP and to a lesser extent TPSSh energies were inconsistent with experiment for the oxidized [Fe3S4]+ cluster. BP86 (and to a slightly lesser extent TPSS) was within expected theoretical and experimental uncertainties for all oxidation states, the only qualitative error being 5kJ/mol in favor of the M(S)=3/2 configuration for the [Fe3S4]+ cluster, so BP86 was used for quantitative results. Computed reorganization energies and reduction potentials point directly towards the [Fe3S4] cluster as the superior choice of electron carrier, with the [ZnFe2S4] cluster a close second. In addition, partially and fully Mo-substituted clusters were investigated and found to have very low reorganization energies but too negative reduction potentials. The results provide a direct rationale why any substitution weakens the cluster as an electron carrier, and thus why the [Fe3S4] composition is optimal in the biological clusters.
authors.affiliation: Technical University of Denmark, Department of Chemistry, Building 207, 2800 Kgs. Lyngby, DK, Denmark. kpj@kemi.dtu.dk
authors.forename: Kasper P
authors.initials: KP
authors.lastname: Jensen
mesh_terms: D019295:Computational Biology; D003198:Computer Simulation; D004578:Electron Spin Resonance Spectroscopy; D007501:Iron / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008670:Metals / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D007506:Iron-Sulfur Proteins; D008670:Metals; D007501:Iron