The Origin of the Photoluminescence Enhancement of Gold‐Doped Silver Nanoclusters: The Importance of Relativistic Effects and Heteronuclear Gold–Silver Bonds

Abstract The weak photoluminescence of silver nanoclusters prevents their broad application as luminescent nanomaterials. Recent experiments, however, have shown that gold doping can significantly enhance the photoluminescence intensity of Ag 29 nanoclusters but the molecular and physical origins of this effect remain unknown. Therefore, we have computationally explored the geometric and electronic structures of Ag 29 and gold‐doped Ag 29− x Au x ( x= 1–5) nanoclusters in the S 0 and S 1 states. We found that 1) relativistic effects that are mainly due to the Au atoms play an important role in enhancing the fluorescence intensity, especially for highly doped Ag 26 Au 3 , Ag 25 Au 4 , and Ag 24 Au 5 , and that 2) heteronuclear Au−Ag bonds can increase the stability and regulate the fluorescence intensity of isomers of these gold‐doped nanoclusters. These novel findings could help design doped silver nanoclusters with excellent luminescence properties.