Infrared studies on polymorphs of silicon dioxide and germanium dioxide

The infrared spectra of coesite, low-temperature tridymite, low-temperature cristobalitelow-~emperature quartz, vitreous silica, hexagonal Oe02, tetragonal Ge02, and vitreous germallla are reported from ~,OOO to 300 C~-l. Wherever possible an assignment of frequencies has been made on t he basls of the selectlOn rules for the crystal symmetry. Three characteris.tic gro up frequencies. near 1,lOq, 800, and 480 cm-1 are common to all the polymorphs of Sl02. Thes.e frequ~nCle.s respectlvely correspond to a str~tching mode involving displacements assoclated prnnanly wlth the oxygen atoms, a stretclung mode involving displacements associated primarily . wi~h the. sil~co~ atoms, and a Si-O bending mode. The presence of these group frequencles III coeslte mdlcates that t he coordination of silicon in coesite is tetrahedral and that its high density is associated with the packinrr of tetrahedral units at an angle approximatiI?g 120 degrees .. The tetragonal and hexagon~l GC02 polymorphs show a marked dlfference III spectra due III part to the change from sixfold to fourfold coordination. The assignment of obscrved frequencies in hexagonal Ge02 is consistent with that made for low-temperature quartz if allowance is made for the heavier mass of t he Ge atom.