Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters

Structures, energetics, and electronic properties of noble metal-doped germanium (MGe_n with M = Cu, Ag, Au; n = 1-19) clusters are systematically investigated by using the density functional theory (DFT) approach. The endohedral structures in which the metal atom is encapsulated inside of a germanium cage appear at n = 10 when the dopant is Cu and n = 12 for M = Ag and Au. While Cu doping enhances the stability of the corresponding germanium frame, the binding energies of AgGe_n and AuGe_n are always lower than those of pure germanium clusters. Our results highlight the great stability of the CuGe₁₀ cluster in a D_4d structure and, to a lesser extent, that of AgGe₁₅ and AuGe₁₅, which exhibits a hollow cage-like geometry. The sphere-type geometries obtained for n = 10-15 present a peculiar electronic structure in which the valence electrons of the noble metal and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. It is found that the coinage metal is able to give both s- and d-type electrons to be reorganized together with the valence electrons of Ge atoms through a pooling of electrons. The cluster size dependence of the stability, the frontier orbital energy gap, the vertical ionization potentials, and electron affinities are given.