A series of quasi-icosahedral gold fullerene cages: Structures and stability

•An icosahedron-based template has been proposed for icosahedral Aun cages.•Two new, large cages for Au92 and Au122 have good stability with Ih symmetry.•The HOMO–LUMO gaps of the Au92 and Au122 cages are suggested strong metallicity.•Analyses of the electronic orbitals show sp–d hybridization in the two Aun cages.

An icosahedron-based template has been proposed and applied to produce a series of initial icosahedral Aun (n=32, 42, 72, 92, and 122) cages. Relativistic density functional theory calculations have subsequently been performed on these structures. The results show that two new, large cages for Au92 and Au122 have good stability, and that the optimized cages with Ih symmetry are quasi-icosahedron and low-lying in energy. Moreover, the HOMO–LUMO gaps of the Au92 and Au122 cages are very small, suggesting strong metallicity. Analyses of the electronic orbitals show sp–d hybridization in the Au92 and Au122 cages.