Effect of single electrons on the excited state dynamics of rod-shaped Au₂₅ nanoclusters

The excited state dynamics of small-sized metal nanoclusters are dependent on their crystal structures, while the effect of the charge state remains largely unknown. Here, we report the influence of single electrons on the excited-state dynamics of non-superatom Au clusters by comparing the transient absorption isotropy and anisotropy dynamics of two rod-shaped Au₂₅ nanoclusters protected by organic ligands. Two decay lifetimes (0.9 ps and 2.3 μs) can be identified in the excited state relaxation of Au₂₅²⁺ rods, which are assigned to the internal conversion from a higher to lower excited state and the relaxation to the ground state, respectively. With the addition of one electron, an additional 660 ps decay is observed in Au₂₅⁺, which should originate from the presence of a single electron occupied molecular orbital. Transient anisotropy measurements reveal a 500 ps rotational diffusion process in both the nanoclusters, while the initial dipole moment orientation is found to be highly dependent on the charge state. These results are of importance to understanding the effect of the charge state on the optical properties of metal nanoclusters.