An important component of the effort to improve solar energy conversion is the water oxidation 2H2O ? O2+ 4H+ + 4e- to form dioxygen, often catalyzed by inorganic complexes. One prominent, successful catalytic complex is the ruthenium �blue dimer'[(bpy)2(H2O)RuIIIORuIII(H2O)(bpy)2]4+, where bpy denotes bipyridine. The catalytically competent species responsible for the initial step in dioxygen formation is [(bpy)2(O)RuVORuV(O)(bpy)2]4+ (produced by blue dimer repeated oxidation by Ce4+). The LHS and RHS of this complex each carry an oxyl group RuV=O. We will describe our efforts to elucidate the unknown mechanism of O2 production via a DFT study of this reacting system surrounded by ~ 70 classical explicit waters and including four quantum waters, two of which form a short chain connecting the LHS and RHS oxo groups. The roles of a water proton relay chain, the oxo bridge and the surrounding solvent will be highlighted.

On the mechanism of water oxidation by the blue dimer

242nd National Meeting (2011)

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