Charging Effects on Bonding and Catalyzed Oxidation of CO on Au8 Clusters on MgO

Gold octamers (Au8) bound to oxygen-vacancy F-center defects on Mg(001) are the smallest clusters to catalyze the low-temp. oxidn. of CO to CO2, whereas clusters deposited on close-to-perfect magnesia surfaces remain chem. inert. Charging of the supported clusters plays a key role in promoting their chem. activity. IR measurements of the stretch vibration of CO adsorbed on mass-selected gold octamers soft-landed on MgO(001) with coadsorbed O2 show a red shift on an F-center-rich surface with respect to the perfect surface. The expts. agree with quantum ab initio calcns. that predict that a red shift of the C-O vibration should arise via electron back-donation to the CO antibonding orbital. [on SciFinder(R)

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