Modeling the Catalyst Activation Step in a Metal-Ligand Radical Mechanism Based Water Oxidation System

Designing catalysts for water oxidation (WOCs) that operate at low overpotentials plays an important role in developing sustainable energy conversion schemes. Recently, a mononuclear ruthenium WOC that operates via metal–ligand radical coupling pathway was reported, with a very low barrier for O–O bond formation, that is usually the rate-determining step in most WOCs. A detailed mechanistic understanding of this mechanism is crucial to design highly active oxygen evolution catalysts. Here, we use density functional theory based molecular dynamics (DFT-MD) with an explicit description of the solvent to investigate the catalyst activation step for the [Ru(bpy) ₂ (bpy–NO)] ²⁺ complex, that is considered to be the rate-limiting step in the metal–ligand radical coupling pathway. We find that a realistic description of the solvent environment, including explicit solvent molecules and thermal motion, is crucial for an accurate description of the catalyst activation step, and for the estimation of the activation barriers