A Comparison Of The Chemical Bonding And Reactivity Of Si8h8o12 And Ge8h8o12: A Theoretical Study

We have analyzed the chemical bonding and reactivity in the cubic molecule octahydridosilsesquioxane, Si8H8O12, and its counterpart Ge8H8O12 by means of ab initio quantum chemical methods and group theory. Density functional theory and MP2 methods combined with the basis sets 6-311+G(d) and 6-311++G(2d,p) were used for geometry optimization and vibrational frequency analysis. The geometries of Si8H8O12 and Ge8H8O12 are unstable under O-h symmetry and distort to the rare T-h molecular symmetry. The energy gained from this pseudo-Jahn-Teller distortion ranges from 0.78 to 6.14 kcal mol(-1) depending on methodological treatment. The Fukui functions and the molecular electrostatic potential were both used as DFT-based reactivity descriptors. Our study shows that Si8H8O12 and Ge8H8O12 are both hard amphoteric molecules. The cavity within each cage is acidic and able to encapsulate hard small bases such as F-. The exterior of the cages is basic and can form stable exohedral complexes with hard acids, as in the case of H+. The insertion of F- in Si8H8O12 and Ge8H8O12 cages gives the most stable endohedral complexes of the series studied, characterized by formation energies of -3.50 and -3.45 eV at CAM-B3LYP/6-311+G(d) and -3.61 and -3.68 eV at the MP2/6-311++G(d,p) level, respectively. The calculated formation energies of the exohedral and endohedral complexes align with the DFT reactivity descriptor analysis.