Assessment of density functional theory methods for the [FeFe]-hydrogenases-inspired molecular catalysts

Abstract

Enzymes, as the result from natural evolution, have greatly inspired chemists to design high-performance catalysts for various reactions. For such design, theoretical calculations under the scheme of density functional theory have been extensively used, but the quality strongly depends on the chosen functional. Herein, we evaluated the reliability of six functionals, including BP86, B3LYP, PBE, PBE0, TPSS and TPSSh, for theoretical investigation of [FeFe]-hydrogenases-based catalysts. By comparing with experimental data, pure functionals, especially PBE functional, showed the best performance in terms of redox potential calculation, with R-square of 0.95. Also, PBE functional showed slightly better in predicting geometry of [FeFe] molecular catalysts than the others. This assessment supports PBE functional to be widely used in predicting both geometry and energy for [FeFe]-hydrogenases-inspired molecular catalysts.