Experimental and theoretical investigation of the electronic and geometrical structures of the Au32 cluster.

Photoelectron spectroscopy and theoretical calculations are used to elucidate the structure of the Au?? - cluster. Although density functional calculations suggest that the high symmetry Ih cage structure of Au?? remains to be the lowest in energy for Au?? - at 0 K, the calculated photoelectron spectrum of a low-lying amorphous structure (C?) is found to agree best with the experiment. Free energy calculations show that the C? structure becomes the most stable isomer at higher temperatures, indicating the importance of entropy in determining the stability of clusters at finite temperatures.

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