Development of Accurate DFT Methods for Computing Redox Potentials of Transition Metal Complexes: Results for Model Complexes and Application to Cytochrome P450

摘要: Single-electron reduction half potentials of 95 octahedral fourth-row transition metal complexes binding a diverse set ligands have been calculated at the unrestricted pseudospectral B3LYP/LACV3P level theory in continuum solvent. Through systematic comparison experimental and potentials, it is determined that B3LYP strongly overbinds d-manifold when coordinates interacting underbinds weakly ligands. These error patterns give rise to an extension localized orbital correction (LOC) scheme previously developed for organic molecules which was recently extended spin-splitting properties organometallic complexes. Mean unsigned errors redox are reduced from 0.40 ± 0.20 V (0.88 max error) 0.12 0.09 (0.34 using simple seven-parameter model. Although focus this article on complexes, we ...