CNDO-2 MOLECULAR-ORBITAL STUDY OF THE SILICA POLYMORPHS QUARTZ, CRISTOBALITE, AND COESITE

CNDO/2 MO calculations on H12Si5O16 clusters modeling silicate tetrahedral linkage in the silica polymorphs show total energy minima at bent SiOSi angles and a correlation between the Si-O bond lengths, d(Si-O), used in the calculation and the minimum energy value of the SiOSi angle. Calculations on hydrogen saturated Si5O16 clusters isolated from the structures of low quartz, low cristobalite and coesite which were adjusted by DLS methods so that all d(Si-O) equal 1.61 Å and all LOSiO equal 109.47° yield Mulliken bond overlap populations, n(Si-O), and Si-O two-center energies, E(Si-O), which correlate with observed bond lengths; shorter bonds involve larger n(Si-O) values and more negative E(Si-O) values. © 1979 Springer-Verlag.