Ultrathin MgO films grown on Ag(001) have been investigated using X-ray and ultraviolet photoemission spectroscopies for oxide films successively exposed to Mg and O₂ flux. Studying work functions and layer-resolved Auger shifts allows us to keep track of band profiles from the oxide surface to the interface and reveal the charge- transfer mechanisms underlying the controlled creation of Mg-induced surface color centers and the catalytic enhancement of O₂ activation. Our results demonstrate that one can intimately probe the catalytic properties of metal-supported ultrathin oxide films by studying the electronic band alignment at interfaces
