The structural evolution of negatively charged gold clusters (Au(n)(-)) in the medium size range for n = 27-35 has been investigated using photoelectron spectroscopy (PES) and theoretical calculations. New PES data are obtained using Ar-seeded He supersonic beams to achieve better cluster cooling, resulting in well-resolved spectra and revealing the presence of low-lying isomers in a number of systems. Density-functional theory calculations are used for global minimum searches. For each cluster anion, more than 200 low-lying isomers are generated using the basin-hopping global minimum search algorithm. The most viable structures and low-lying isomers are obtained using both the relative energies and comparisons between the simulated spectra and experimental PES data. The global minimum structures of Au(n)(-) (n = 27, 28, 30, and 32-35) are found to exhibit low-symmetry core-shell structures with the number of core atoms increasing with cluster size: Au(27)(-), Au(28)(-), and Au(30)(-) possess a one-atom core; Au(32)(-) features a three-atom triangular core; and Au(33)(-) to Au(35)(-) all contain a four-atom tetrahedral core. The global searches reveal that the tetrahedral core is a popular motif for low-lying structures of Au(33)(-) to Au(35)(-). The structural information forms the basis for future chemisorption studies to unravel the catalytic effects of gold nanoparticles.

How nanoclusters transform from one structural type to another as a function of size is a critical issue in cluster science. Here we report a study of the structural transition from the golden cage Au(16)(-) to the pyramidal Au(20)(-). We obtained distinct experimental evidence that the cage-to-pyramid crossover occurs at Au(18)(-), for which the cage and pyramidal isomers are nearly degenerate and coexist experimentally. The two isomers are observed and identified by their different interactions with O(2) and Ar. The cage isomer is observed to be more reactive with O(2) and can be preferentially "titrated" from the cluster beam, whereas the pyramidal isomer has slightly stronger interactions with Ar and is favored in the Au(18)Ar(x)(-) van der Waals complexes. The current study allows the detailed structural evolution and growth routes from the hollow cage to the compact pyramid to be understood and provides information about the structure-function relationship of the Au(18)(-) cluster.

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,Cu͒ 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 substitution͒ 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.