Rational design of the 6e thiolate-protected Au₂₄(SR)₁₈ nanocluster

Abstract The growth mechanism of thiolate-protected gold nanoclusters (AuNCs) has been advanced, but precise crystal structure information is lacking. Recent mass spectrometry and nuclear magnetic resonance analysis experiments traced the Au 24 (SR) 18 cluster as a non-negligible byproduct intermediate during the reaction between [Au 25 (SR) 18 ] − , the flagship cluster of the remarkable nanocluster ship, and Au 25 (SR) 19 , a cluster with 25 Au atoms but featuring a completely different structure than the [Au 25 (SR) 18 ] − cluster. However, the precise structure of the Au 24 (SR) 18 cluster is unknown. In this study, a total of seven Au 24 (SR) 18 isomers were constructed using the grand unified model. Density functional theory calculations demonstrated that two of them could be considered quasi-degenerate suggesting that both might coexist in experiments. Geometrical features, electronic structures, and absorption spectra were calculated for potential future comparisons. This work contributes to fully interpreting the growth mechanism of AuNCs .