DFT Investigation of Models Related to the Active Siteof Hydrogenases

From a methodological perspective, most quantum-chemical studies of hydrogenases and related models have been carried out within the theoretical framework of the density functional theory (DFT), a choice that stems principally from the very good trade-off between the accuracy of DFT and its relatively low computational cost. This chapter presents a non comprehensive overview of quantum mechanics (QM) studies of molecular models related to the active site of hydrogenases and aims to show how computational studies have contributed to the elucidation of key properties of hydrogenases, as well as of related synthetic compounds. When considering biomimetic models, recent results have highlighted the importance of coupled proton-electron transfer for efficient H2 formation or oxidation, and computational studies are expected to play an important role in the design of novel and more efficient synthetic catalysts.