Using the density functional theory at the BLYP level with the DNP (DN basis with polarization functions) basis sets, the geometric structures, stability and electronic structures of MSin (M=Sc, Ti, V n=8-16) have been investigated theoretically. Furthermore the growth behavior of metal-doped silicon clusters is found.For ScSin (n=8-16), they tend to form basketlike structures when n<14 , while they tend to form cage-like structure, encapsulating Sc atom in the cage, when n≥14. The energy of the fullerene-like structure of Sc@Si16 is the lowest one among several different isomers. Furthermore, we found f-Sc@Si16 is of an open shell structure with one μB of spin, and 3.323eV adiabatic affinity energy. Therefore f-Sc@Si16 tends to form its anion with closed shell structure by getting an electron.For TiSin (n=8-16), the basketlike structure is of the best stability when n is less than13, while the cage-like structure begin to possess higher binding energy when n ≥13, in good agreement with the case that the ability of TiSin (n=13, 15, 16) clusters reacting with water decreases due to their closed cage-like structure in experiment.For VSin (n=8-16), the clusters will be the stable basketlike structure when n is less than 12. But they are easy to form the stable cage-like structures when n equal to or greater than 12. Furthermore we found f-V@Si16 is of an open shell structure, so it's easy losing an electron to form f-V@Si16+ with closed shell structure. |