Chemical Involvement of Solvent Water Molecules in Elementary Steps of the Fenton Oxidation Reaction.

The spontaneous formation of the contested ferryl ion is evident in ab initio molecular dynamics calculations on the Fe /H O system in aqueous solution (Fenton reagents). Not only is the ferryl ion preferred over the hydroxyl radical as the active oxidative species, but the solvent water molecules play a crucial role in the mechanism. The picture shows the unit cell containing the iron complex surrounded by solvent water molecules 1.8 ps after the start of the simulation, when the ferryl ion is being formed (blue: iron, red: oxygen, white: hydrogen).