Modification of vacuum-ultraviolet absorption of SiOH groups in SiO2 glass with temperature, F2 laser irradiation, and H–D isotope exchange

Variations of vacuum-ultraviolet (VUV) absorption of silanol (SiOH) groups in synthetic wet SiO2 glass with temperature, exposure to F2 laser light, and with H–D isotope exchange were examined at photon energies below 8 eV. The intensity of the VUV absorption band decreases with cooling or with exposure to F2 laser light. The spectral changes in both cases are qualitatively similar and are attributed to an alternation of the bonding configuration of SiOH groups from isolated into hydrogen-bonded states. However, the resultant states are distinctly different: the hydrogen-bonded state formed on cooling is restored reversibly to the isolated state on heating, while that induced by F2 laser light is metastable and does not decay below 300 °C. The VUV absorption is also reduced by replacing SiOH groups with SiOD groups due to the decrease of the zero-point energy of the ground state associated with OH groups.