Theoretical study of geometric and electronic structures, and anion PES of the (n = 5–11; m = 1–3) clusters

The correlation between the features of the geometric and electronic structures and the anion photoelectron spectra (PES) of Al n Cs m - (n = 5–11; m = 1–3) were investigated using DFT calculations. The geometric changes from the octahedral to the wheel-like (or semi-icosahedral) structure were found in the n = 8 and 9 AlnCs− clusters, and the n = 7 and 8 Al n Cs 2 - and Al n Cs 3 - clusters. The calculated vertical detachment energy (VDE) was in good agreement with the corresponding anion PES. The Kohn–Sham orbital energy gap of the 3p orbital region in the wheel-like structure was narrower than that in the octahedral structure.