Electronic shells of a tubular Au₂₆ cluster: a cage-cage superatomic molecule based on spherical aromaticity

Gold clusters, which display a variety of unusual geometric structures due to their strong relativistic effects, have attracted much attention. Among them, Au₂₆ has a high-symmetry tubular structure (D_6d) with a large HOMO-LUMO energy gap, but its electronic stability still remains unclear. In this paper, the electronic nature of the Au₂₆ cluster is investigated using the density functional theory method. Depending on the super valence bond model, the tubular Au₂₆ cluster with 26 valence electrons could be viewed as a superatomic molecule composed of two open cages based on spherical aromaticity, and its molecule-like electronic shell closure is achieved via a super triple bond (σ, 2π) between the two cages. Based on this new cage-cage superatomic structural model, a series of similar tubular clusters are predicted from the Au₂₆ skeleton. The two capped Au atoms are replaced by Cu, Ag and In atoms, respectively, to form tubular D_6d Au₂₄Cu₂ and Au₂₄Ag₂ (26e) and Au₂₄In₂ (30e) clusters, where the super triple bonds also exist. Moreover, tubular D_5d Au₂₀In₂ (26e) is obtained by replacing hexatomic Au₆ rings in the bulk of Au₂₄In₂ with pentagonal Au₅ rings. Chemical bonding analysis reveals that there is a super quintuple bond (σ, 2π, 2δ) between two open (Au₁₀In) cages, in accordance with the 26e Li₂₀Mg₃ superatomic molecule composed of two icosahedral superatoms. Our study proposes the new cage-cage structural model of superatomic molecules based on spherical aromaticity, which extends the range of the super valence bonding pattern and gives inferences for further study of superatomic clusters.