Theoretical study of structural and electronic properties of H-silsesquioxanes

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The results of first principles calculations on H-silsesquioxanes (i.e., (HSiO3/2)n with n = 4, 6, 8, 10, 12, 14, and 16) are reported here. Double numeric basis sets and local and nonlocal density approximations to density functional theory are employed for calculations. It is shown that use of the nonlocal density approximation is required for the reliable prediction of the most stable isomer for silsesquioxanes. Furthermore, a progression of the preferred building unit with the increase in size of the T cage is revealed. The smaller T cages prefer four- and five-member rings while the larger cages are found to prefer four- and six-member rings. Analysis of the energy of the hydrolysis reaction, binding energy, and fragmentation paths finds the relative stability of the silsesquioxane cages containing four-, five-, and six-member rings in agreement with experimental observations. For the (HSiO3/2)16 cage, the calculated results predict the stability of the D2d-645046 configuration over the D4d-605842 configuration in contradiction to suggestions based on 29Si NMR measurements. We find a consistent picture for the highest occupied molecular orbitals (HOMOs) of all silsesquioxanes considered showing them to be composed of (lone-pair) oxygen p-type atomic orbitals. On the other hand, the lowest unoccupied molecular orbitals (LUMOs) show size dependence in their composition which appears to cause the presence of a state in the HOMO-LUMO gap for higher silsesquioxane cages. Density of states plots and analysis of molecular orbitals reveal this state to be due to the terminal hydrogens bonded to silicon atoms.

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Journal of Physical Chemistry B