Theoretical Prediction of Optical Absorption and Emission in Thiolated Gold Clusters

Although the photoluminescence of gold clusters has been extensively studied so far, there are still questions on the origin of the emission in these materials. In this work, we report time-dependent density functional theory calculations on the absorption and emission spectra of the well-studied Au₂₅(SR)₁₈^- cluster, the lowest energy isomer of the Au₃₈(SR)₂₄ cluster, and five isomers of the Au₂₂(SR)₁₈ cluster. Good agreement between the calculated and measured absorption spectra, as well as with the lowest-energy emission values for these clusters, was demonstrated, verifying the accuracy of the theoretical methods employed. Our results for Au₂₅(SR)₁₈^- explain a newly observed feature in the absorption peak, also rationalizing the optical response in terms of the superatom model. The analysis of the absorption and emission characteristics of the Au₂₅(SR)₁₈^- and Au₃₈(SR)₂₄ clusters provides an estimate of the spectral regions, where fluorescence or phosphorescence is predicted to occur. Interestingly, we find that for Au₂₂(SR)₁₈, one of the five proposed structures could be present at a significant concentration in the sample, even though it is not the lowest in energy structure, which can be explained, in part, by solvent effects.