The optical constants of quartz, vitreous silica and neutron-irradiated vitreous silica: (II) Analysis of the infrared spectrum of vitreous silica

Abstract

Optical constant data for vitreous silica and neutron-irradiated vitreous silica, given in part I are examined in an attempt to gain further knowledge of the structure of the glass. Strong features of the spectrum can be described by band broadening parameters, which are calculated using an extension of the Wilson GF matrix method, and are shown to be quantitatively related to the distribution of SiO distances and oxygen bond angles obtained from X-ray scattering data. The approximation commonly used to generate the optically active vibrational spectra of glasses, namely to form the product of the vibrational density of states function and a weakly frequency-dependent intensity factor gives a relatively poor representation of the experimental spectrum. The magnitude of ‘disorder-induced’ absorption in regions well away from the major bands is semi-quantitatively estimated by subtracting the contributions of the major bands. Interpretation of some of the features of this difference spectrum is possible in terms of vibrations of non-bridging oxygen atoms, but if this interpretation is correct, it is necessary to postulate clustering of ‘dangling’ oxygen atoms, which would not be consistent with a random network model for the structure. An alternative explanation, that the vibrations are framework modes, leads to the conclusion that the preferred configuration in vitreous silica resembles the arrangement of silicon-oxygen tetrahedra in cristobalite.