Isomer identification and resolution in small gold clusters

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A variety of experimental techniques are used to resolve energetically close isomers of Au(7)(-) and Au(8)(-) by combining photoelectron spectroscopy and ab initio calculations. Two structurally distinct isomers are confirmed to exist in the cluster beam for both clusters. Populations of the different isomers in the cluster beam are tuned using Ar-tagging, O(2)-titration, and isoelectronic atom substitution by Cu and Ag. A new isomer structure is found for Au(7)(-), which consists of a triangular Au(6) unit with a dangling Au atom. Isomer-specific photoelectron spectra of Au(8)(-) are obtained from O(2)-titration experiment. The global minimum and low-lying structures of Au(7)(-), Au(8)(-), and MAu(n)(-) (n=6,7; M=Ag,Cu) are obtained through basin-hopping global minimum searches. The results demonstrate that the combination of well-designed photoelectron spectroscopy experiments (including Ar-tagging, O(2)-titration, and isoelectronic substitution) and ab initio calculation is not only powerful for obtaining the electronic and atomic structures of size-selected clusters, but also valuable in resolving structurally and energetically close isomers of nanoclusters.