Unraveling structures of protection ligands on gold nanoparticle Au(68)(SH)(32)

New low-energy atomic structures of the thiolate-protected gold nanoparticle Au(68)(SH)(32) are uncovered, where the atomic positions of the Au atoms are taken from the recent single-particle transmission electron microscopy measurement by Kornberg and co-workers, whereas the pattern of thiolate ligands on the gold core is attained on the basis of the generic formulation (or rule) of the “divide and protect” concept. Four distinct low-energy isomers, Iso1 to Iso4, whose structures all satisfy the generic formulation, are predicted. Density-functional theory optimization indicates that the four isomers are all lower in energy by 3 to 4 eV than the state-of-the-art low-energy isomer reported. Further analysis of the optimized structures of Au(68)(SH)(32) shows that the structure of gold core in Iso1 to Iso4 is consistent with the experiment, whereas the positions of a few Au atoms at the surface of gold core are different. The computed optical absorption spectra of the four isomers are consistent with the measured spectrum. Computation of catalytic properties of Au(68)(SH)(32) toward CO oxidation suggests that the magic number cluster can be a stand-alone nanoscale catalyst for future catalytic applications.