A comparative study of structural, electronic, and optical properties of thiolated gold clusters with icosahedral vs...

The structural, electronic, and optical properties of the protected Au clusters with icosahedral (Ih) and face-centered cubic (FCC)-like Au₁₃ cores were studied to understand the origin of the difference in the optical gaps of these clusters. It has been demonstrated that the choice of density functionals does not qualitatively affect the properties of Au₂₃ and Au₂₅ clusters with Ih and FCC cores. The density of states, molecular orbitals, and natural charges were analyzed in detail using the B3LYP functional. The substantial energy difference in the lowest-energy absorption peaks for the clusters with the Ih and FCC cores is attributed to the difference in the natural charges of the central Au atoms (Au_c) in the Ih and FCC cores, the former of which is more negative than the latter. Natural population analysis demonstrates that the excess negative charge of the Au_c atom in clusters with Ih cores occupies the 6p atomic orbitals. This difference in Au_c is attributed to the smaller size of the Ih core compared to the FCC core, as a less bulky ligand allows a smaller core with increased electron density, which, in turn, increases the highest occupied molecular orbital energy and decreases the optical gap.