Origin of Photoluminescence of Ag25(SR)18– Nanoparticles: Ligand and Doping Effect

Abstract

Recent theoretical insights into the origin of photoluminescence of thiolate-protected gold nanoclusters raise the question of whether the observed luminescence mechanism is valid for related silver nanoparticles. To this end, we perform density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations on the Ag25(SR)18– (R = H, PhMe2) nanocluster, which is currently the only thiolate-protected silver cluster that has a matching analogue in gold. The geometric and electronic structural modifications of Ag25(SH)18– upon photoexcitation are found to be similar but less pronounced than those of Au25(SH)18– at the same level of theory. The Stokes shift is calculated to be 0.37 eV and the replacement of R = H model ligands by R = PhMe2 decreases the Stokes shift in contrast to the increase in Stokes shift for aliphatic ligands previously observed in the Au25 system. The calculated emission energy agrees well with the experimental photoluminescence energy when the typical underes...