Exploration of H2 binding to the [NiFe]-hydrogenase active site with multiconfigurational density functional theory

Abstract

The combination of density functional theory (DFT) with a multiconfigurational wave function is an efficient way to include dynamical correlation in calculations with multiconfiguration self-consistent field wave functions. These methods can potentially be employed to elucidate reaction mechanisms in bio-inorganic chemistry, where many other methods become either too computationally expensive or too inaccurate. In this paper, a complete active space (CAS) short-range DFT (CAS–srDFT) hybrid was employed to investigate a bio-inorganic system, namely H₂ binding to the active site of [NiFe] hydrogenase. This system was previously investigated with coupled-cluster (CC) and multiconfigurational methods in the form of cumulant-approximated second-order perturbation theory, based on the density matrix renormalization group (DMRG). We find that it is more favorable for H₂ to bind to Ni than to Fe, in agreement with previous CC and DMRG calculations. The accuracy of CAS–srDFT is comparable to both CC and DMRG, despite much smaller active spaces were employed than in the corresponding DMRG calculations. This enhanced efficiency at the smaller active spaces shows that CAS–srDFT can become a useful method for bio-inorganic chemistry.