Unraveling the Atomic Structures of 10-Electron (10e) Thiolate-Protected Gold Nanoclusters: Three Au₃₂(SR)₂₂ Isomers, One Au₂₈(SR)₁₈, and One Au₃₃(SR)₂₃

Abstract

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.

Exploration of the Atomic Pathway of Seed-Mediated Growth from Icosahedral [Au25(SR)18]− to Bi-Icosahedral Au38(SR)24 and Au44(SR)26 Clusters Based on the 2e– Hopping Mechanism

“…Herein, we use our recently proposed “2 e – -unit decomposition strategy” to study the structure of 10 e – [Au 29 (SR) 20 ] − and 12 e – [Au 33 (SR) 22 ] − clusters. It is worth noting that many similar size gold clusters, such as Au 29 (SR) 19 , Au 28 (SR) 18 , Au 33 (SR) 22 , Au 29 (SR) 21 , Au 30 (SR) 22 , and Au 32 (SR) 24 , have been theoretically predicted. However, the predicted atomic packing configuration of these clusters is fcc configuration, which is poorly correlated with the icosahedral Au 25 and bi-icosahedron Au 38 clusters.…”