Abstract: | The interaction of bare iron mono‐ and dications with hydrogen peroxide in the gas phase is studied by ab initio calculations employing the B3LYP/6‐311+G* level of theory. For the monocation, the quartet and sextet coordination complexes Fe(H2O2) are high‐energy isomers that easily interconvert to the more stable iron dihydroxide monocation Fe(OH) and hydrated iron oxide (H2O)FeO+ (quartet) or dissociate into FeOH++OH. (sextet). On the dication surface, however, the order of stabilities is reversed in that Fe(H2O2)2+ (quintet) corresponds to the most stable doubly charged species, while the formal FeIV compounds Fe(OH) and (H2O)FeO2+ are higher in energy. |