The Structure-Property Correlations in the Isomerism of Au21 (SR)15 Nanoclusters by Density Functional Theory Study.

Isomerism of atomically precise noble metal nanoclusters provides an excellent platform to investigate the structure-property correlations of metal nanomaterials. In this study, we performed density functional theory (DFT) and time-dependent (TD-DFT) calculations on two Au21 (SR)15 nanoclusters, one with a hexagonal closed packed core (denoted as Au21 hcp ), and the other one with a face-centered cubic core (denoted as Au21 fcc ). The structural and electronic analysis on the typical Au-Au and Au-S bond distances, bond orders, composition of the frontier orbitals and the origin of optical absorptions shed light on the inherent correlations between these two clusters.