LAUSR

Enormous progress has been made in catalytic oxidation reactions involving nanosized gold particles. However, the reaction mechanism of O2 with neutral gold clusters remains complicated. Here, we have performed an unbiased structure search for AunQ and AunO2Q (n = 2–10, Q = 0, −1) clusters by means of CALYPSO structure searching method. Subsequently, the lowest-energy candidate structures were fully optimized at the B3PW91/Au/LANL2DZ/O/6-311+G(d) level of theory to determine the global minimum structures. Based on the ground-state structures of Aun– and AunO2– (n = 2–10), we have simulated the photoelectron spectra (PES) using time-dependent density functional theory. The good agreement between simulated PES and the corresponding experimental data suggest that the current ground-state structures are the true minima. The locally maximized value of the adsorption energy in Au5O2, where the unpaired electron of Au5 can transfer to O2, makes it the most promising candidate of the chemisorbed complex. A compre...