Revisiting the structural and electronic properties of neutral, mono- and di-anionic titanium-doped silicon clusters TiSin0/-/2- (n=6-16)

摘要

The systematic structures search for neutral and Zintl anionic Ti-doped silicon clusters TiSin0/-/2- (n = 6-16) have been carried out using the ABCluster global search technique combined with a double-hybrid density functional method. Based on the predicted energies, adiabatic electron affinities, vertical detachment energies and the consistency between simulated and experimental photoelectron spectroscopy, the true global minimum structures are confirmed. The results show that structural growth pattern of neutral TiSin clusters is from linked structures (n = 10-12) to encapsulated configurations (n = 13-16). In contrast, the evolution pattern of Zintl anionic TiSin-/2- clusters begins with the pentagonal bipyramid structure (n = 6). As the Si atoms increase, these Si atoms attach to the surface adjacent to Ti atom, and gradually surround Ti atom. Eventually, the encapsulated structure is formed when n = 12. Moreover, two extra electrons not only perfect the structure of TiSi12 but also improve its chemical and thermodynamic stability.