Thiolate-protected gold nanoclusters have been investigated intensely due to their fundamental properties and their possible applications. The incorporation of heteroatom(s) into gold nanoclusters has been shown as a promising strategy to synthesize new nanoclusters, while enabling control and enhancement for the desired properties of native gold nanoclusters. Additionally, X-ray crystal structure studies have been utilized for structure elucidation of the doped systems. On the other hand, the underlying mechanisms responsible for the stability of the new alloy, and the resulting changes in the electronic and geometric structure upon doping are still unclear for most of investigated doped systems. In this theoretical study, we turn our attention to the structural and electronic modifications introduced by the doping of the Au25 nanocluster with group IX and X transition metals. In this aspect, we performed DFT and TDDFT calculations on different isomers and charge states of doped clusters. This investigation was also extended to other dopant atoms to correlate theoretical results with experimental findings. Our results show that d-energy levels originating from dopant atoms and their interactions with the super-atomic orbitals play an important role in energetics and optical properties of the doped clusters. We also investigated the effect of spin-orbit coupling on the electronic structure, energetics and absorption spectra for the doped species in different charge states.

Theoretical investigation of the electronic structure and stability for doped Au25 clusters

255th National Meeting (2018)

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