1. Nanoscale Physics Research Laboratory, School of Physics and Astronomy,
   
2. School of Chemistry, University of Birmingham, Birmingham B15 2TT, UK
   
3. UK SuperSTEM Laboratory, Daresbury Laboratory, Daresbury WA4 4AD, UK
   
4. Beijing Electron Microscopy Centre; Laboratory of Advanced Materials and Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Correspondence to: Z. Y. Li¹ Correspondence and requests for materials should be addressed to Z.Y.L. (Email: ziyouli@nprl.ph.bham.ac.uk).

An unambiguous determination of the three-dimensional structure of nanoparticles is challenging¹. Electron tomography requires a series of images taken for many different specimen orientations². This approach is ideal for stable and stationary structures³. But ultrasmall nanoparticles are intrinsically structurally unstable and may interact with the incident electron beam^{4, 5, 6}, constraining the electron beam density that can be used and the duration of the observation. Here we use aberration-corrected scanning transmission electron microscopy⁷, coupled with simple imaging simulation, to determine with atomic resolution the size, three-dimensional shape, orientation and atomic arrangement of size-selected gold nanoclusters that are preformed in the gas phase and soft-landed on an amorphous carbon substrate. The structures of gold nanoclusters containing 3096 atoms can be identified with either Ino-decahedral, cuboctahedral or icosahedral geometries. Comparison with theoretical modelling of the system suggests that the structures are consistent with energetic considerations. The discovery that nanoscale gold particles function as active and selective catalysts for a variety of important chemical reactions has provoked much research interest in recent years^{8, 9, 10, 11, 12}. We believe that the detailed structure information we provide will help to unravel the role of these nanoclusters in size- and structure-specific catalytic reactions^{11, 12}. We note that the technique will be of use in investigations of other supported ultrasmall metal cluster systems.