Appearance of V-encapsulated tetragonal prism motifs in VSi10− and VSi11− clusters

Abstract

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 Si_n 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.