Adsorption energies of molecular oxygen on Au clusters

The adsorption properties of O-2 molecules on anionic, cationic, and neutral Au-n clusters (n=1-6) are studied using the density functional theory (DFT) with the generalized gradient approximation (GGA), and with the hybrid functional. The results show that the GGA calculations with the PW91 functional systemically overestimate the adsorption energy by 0.2-0.4 eV than the DFT ones with the hybrid functional, resulting in the failure of GGA with the PW91 functional for predicting the adsorption behavior of molecular oxygen on Au clusters. Our DFT calculations with the hybrid functional give the same adsorption behavior of molecular oxygen on Au cluster anions and cations as the experimental measurements. For the neutral Au clusters, the hybrid DFT predicts that only Au-3 and Au-5 clusters can adsorb one O-2 molecule.(C) 2004 American Institute of Physics.