Charging Effects on Bonding and Catalyzed Oxidation of CO on Au ₈ Clusters on MgO

Gold octamers (Au ₈ ) bound to oxygen-vacancy F-center defects on Mg(001) are the smallest clusters to catalyze the low-temperature oxidation of CO to CO ₂ , whereas clusters deposited on close-to-perfect magnesia surfaces remain chemically inert. Charging of the supported clusters plays a key role in promoting their chemical activity. Infrared measurements of the stretch vibration of CO adsorbed on mass-selected gold octamers soft-landed on MgO(001) with coadsorbed O ₂ show a red shift on an F-center–rich surface with respect to the perfect surface. The experiments agree with quantum ab initio calculations that predict that a red shift of the C–O vibration should arise via electron back-donation to the CO antibonding orbital.