Unraveling the Atomic Structures of 10-Electron (10e) Thiolate-Protected Gold Nanoclusters: Three Au(32)(SR)(22) Isomers, One Au(28)(SR)(18), and One Au(33)(SR)(23)

[Image: see text] The atomic structures of 10-electron (10e) thiolate-protected gold nanoclusters have not received extensive attention both experimentally and theoretically. In this paper, five new atomic structures of 10e thiolate-protected gold nanoclusters, including three Au(32)(SR)(22) isomers, one Au(28)(SR)(18), and one Au(33)(SR)(23), are theoretically predicted. Based on grand unified model (GUM), four Au(17) cores with different morphologies can be obtained via three different packing modes of five tetrahedral Au(4) units. Then, five complete structures of three Au(32)(SR)(22) isomers, one Au(28)(SR)(18), and one Au(33)(SR)(23) isomers can be formed by adding the thiolate ligands to three Au(17) cores based on the interfacial interaction between thiolate ligands and gold core in known gold nanoclusters. Density functional theory calculations show that the relative energies of three newly predicted Au(32)(SR)(22) isomers are quite close to two previously reported isomers. In addition, five new 10e gold nanoclusters have large highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) gaps and all-positive harmonic vibration frequencies, indicating their high stabilities.