Electronic and molecular structural dependence of metal oxide cluster reactions with water

The molecular scale interactions that govern the catalytically-driven hydrogen evolution reaction from water can be probed by combining anion photoelectron spectroscopic probes of metal oxide cluster models of heterogeneous catalysts with experimental cluster + water reactivity studies and computational treatment. The application of this multi-prong approach to group 6 transition metal oxides will be described, as well as the extension to near-neighbor heterometallic (group 5/group 6; group 6/group 7) oxide cluster systems. The importance of asymmetric oxidation states and oxophilicities emerge from these studies.