We systematically study the equilibrium geometries and electronic and magnetic properties of Ge and VGe (n = 1-19) clusters using the density functional theory approach within the generalized gradient approximation. Endohedral structures in which the vanadium atom is encapsulated inside a Ge cage are predicted to be favored for n ≥ 10. The dopant V atom in the Ge clusters has not an immediate effect on the stability of small germanium clusters (n < 6), but it largely contributes to strengthen the stability for n ≥ 7. Our study enhances the large stability of the VGe cluster, which presents an O symmetry cagelike geometry and a peculiar electronic structure in which the valence electrons of V and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. Consequently, this cluster is proposed to be a good candidate to be used as the building blocks for developing new materials. The cluster size dependence of the stability, the vertical ionization potentials, and electron affinities of Ge and VGe are presented. Magnetic properties and the partial density of states of the most stable VGe clusters are also discussed.

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