Thiolate‐protected gold nanoclusters: structural prediction and the understandings of electronic stability from first principles simulations

Thiolate‐protected gold nanoclusters ( RS‐AuNCs ) have aroused intensive research interests in field of nanoscience since the breakthroughs in structural determination of Au 102 ( SR ) 44 , Au 25 ( SR ) 18 − , and Au 38 ( SR ) 24 achieved by both theory and experiment. To date, single crystal structures of about 20 thiolate‐protected gold nanoclusters had been successfully resolved. The analysis on the structural patterns of the high symmetric cores and the types and numbers of the protecting ligand motifs in these nanoclusters provides deep insight into the inherent structural rule. On this basis, the developed conceptual models not only rationalize the known structures, but also help to predict new ones. Given that the synthesis and crystallization of RS‐AuNCs in experiment still remain challenging, theoretical calculations based on density functional theory play a crucial role in structural prediction. Herein, three developed conceptual models for explaining electronic stability and the recent progress of structural prediction through first principles simulations are highlighted. As more atomically precise structures of RS‐AuNCs being determined, further understanding of the structure–property relationships is expected to achieve and boost practical applications of metal nanoclusters. WIREs Comput Mol Sci 2017, 7:e1315. doi: 10.1002/wcms.1315 This article is categorized under: Structure and Mechanism > Molecular Structures