Enhanced Stability by Three-Dimensional Aromaticity of Endohedrally Doped Clusters X10M0/- with X = Ge, Sn, Pb and M = Cu, Ag, Au

The group 14 clusters encapsulated by coinage metals in neutral and anionic states X10M0/- (X = Ge, Sn, Pb and M = Cu, Ag, Au) are investigated using quantum chemical calculations with the DFT/B3LYP functional and coupled-cluster CCSD(T) theory. Addition of transition metals into the empty cages forms high symmetry endohedral structures, except for Ge10Ag0/-. In agreement with experiments available for X10Cu, the D-4d global minima of the anions are calculated to be magic clusters with large frontier orbital gaps, high vertical and adiabatic detachment energies, and large embedding energies and binding energies as compared to those of the empty cages X-10(2-). The enhanced stability of these magic clusters can be rationalized by the three-dimensional aromaticity.