The evolution of structural motifs of gold cluster anions, Au-n(-), in the size range n=11-24 has been determined through a comparison of electron diffraction data with density functional calculations. The results provide clear evidence for a transformation from planar to three-dimensional structures in the range n=12-14, the development of cage structures for n=16 and 17, the appearance of a tetrahedral structure at n=20, and the emergence of a highly symmetric tubular structure for n=24.
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