Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid

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 Au16− to the pyramidal Au20−. We obtained distinct experimental evidence that the cage-to-pyramid crossover occurs at Au18−, 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 O2 and Ar. The cage isomer is observed to be more reactive with O2 and can be preferentially “titrated” from the cluster beam, whereas the pyramidal isomer has slightly stronger interactions with Ar and is favored in the Au18Arx− 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 Au18− cluster.