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An optical absorption (OA) band of interstitial dichlorine monoxide molecules with peak at 4.7 eV and halfwidth 0.94 eV is identified in F 2  laser‐irradiated ( ħω  = 7.9 eV) synthetic silica glass bearing both interstitial O 2  and Cl 2  molecules. Alongside with intrinsic defects, this OA band can contribute to solarization of silica glasses produced from SiCl 4 . Although only the formation of ClClO is confirmed by its Raman signature, its structural isomer ClOCl may also contribute to this induced OA band. Thermal destruction of this band between 300 °C and 400 °C almost completely restores the preirradiation concentration of interstitial Cl 2 . An additional weak OA band at 3.5 eV is tentatively assigned to ClO 2  molecules. The strongly forbidden 1272 nm infrared luminescence band of excited singlet O 2  molecules is observed at 3–3.5 eV excitation, demonstrating an energy transfer process from photoexcited triplet Cl 2  to O 2 . The energy transfer most likely occurs between Cl 2  and O 2  interstitial molecules located in neighboring nanosized interstitial voids in the structure of SiO 2  glass network.

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Optical Absorption of Excimer Laser‐Induced Dichlorine Monoxide in Silica Glass and Excitation of Singlet Oxygen Luminescence by Energy Transfer from Chlorine Molecules