Another look at energetically quasi-degenerate structures of the gold cluster Au with q = 1, 0, -1.

Quantum chemical computations were used to reinvestigate the geometries, spectroscopic, and energetic properties of the gold clusters Au in three charge states (q = 1, 0, -1). Density functional theory (DFT) and the domain-based local pair natural orbital modification of the coupled-cluster theory DLPNO-CCSD(T) calculations revealed that, at variance with earlier reports in the literature, while the anion Au tends to exist in a tube-like form, both the lowest-energy Au and Au isomers exhibit a pyramidal shape. However, several isomers were found to lie very close in energy, thus rendering a structural transition and their coexistence easy to occur. More specifically, the equilibrium geometry of the neutral Au is a core-shell pyramid-like structure with one gold atom located inside. We also identified a novel ground state for the anion Au and located for the first time the global minimum of the cation Au . The vertical detachment energies of the neutral and anionic states were also computed and used to assign the available experimental photoelectron spectra. Although many Au isomers were predicted to be energetically quasi-degenerate, the corresponding distinctive vibrational signatures can be used as fingerprints for the identification of cluster geometrical features.