Sila-fulleranes: promising chemically active fullerene analogs

Density-functional theory (DFT) was applied to investigate the geometry and electronic properties of bare Si₆₀ and H-terminated Si-fullerene. DFT predicts outward sites on a bare Si₆₀ cage. By using π -orbital axis analysis (POAV), it is shown that these sites result from a strong tendency of silicon atoms to form sp³ hybridization bonds. Natural bond orbital (NBO) analysis confirms the sp³ hybridization nature of Si–Si bonds in Si-fulleranes. The quantum confinement effect (QCE) does not affect band gap (BG) so strongly in the size between 1 and 1.7 nm. In contrast, the geometry and symmetry of the cage have a significant influence on the BG. In contrast to their carbon analogs, pentagon rings increase the stability of the cages. Functionalized Si-cages are stable and can be chemically very active. The electronic properties are highly sensitive to the surface chemistry via functionalization with different chemical groups. As a result, BGs and chemical activities of these cages can be drastically tuned through the chemistry of the surface. (paper)