Appearance of V-encapsulated tetragonal prism motifs in VSi and VSi clusters.

The structural and electronic properties of V-doped silicon clusters, VSi10-/0 and VSi11-/0, were investigated by using mass-selected anion photoelectron spectroscopy in combination with theoretical calculations. Photoelectron spectroscopy of VSi10- and VSi11- clusters with spectral similarity reveals that the two cluster structures resemble each other. Interestingly, theoretical calculation studies provide definitive evidence of the global minima for the two clusters to be V-encapsulated tetragonal prism motifs with extra Si atoms bicapped and tricapped, respectively. The enhanced stability of the tetragonal prism unit in VSi10- and VSi11- is due to the strong interactions between 3d (V) and 3p (Si) orbitals, and more charge transfers from the Sin framework to the encapsulated V atom. The tetragonal prism unit possessed by both the VSi10- and VSi11- clusters is observed for the first time in the current work, and may offer new ideas in developing components for Si-based nanodevices.