Reply to Comments on “Singlet Oxygen ¹O₂ in Photocatalysis on TiO₂. Where Does It Come from?”

In the Comment the authors Y. Nosaka and A. Y. Nosaka present arguments against the mechanism of singlet oxygen production which was suggested in the earlier published paper (Demyanenko et al., J. Phys. Chem. C 2019, 123, 2175) to explain the experimental data for the Near IR (NIR)-luminescence observed to appear after laser excitation at 355 nm of TiO₂ suspension in air-saturated solvents CCl₄ and H₂O. The main arguments of the Comment are directed against Assignment of the NIR Emission and Electron Photodetachment Mechanism suggested by Demyanenko et al.. Particularly the Comment claims that the red shift (near 30 nm) and bandwidth (50-60 nm) of the NIR luminescence observed in paper by Demyanenko et al. are too large to be assigned to the luminescence of singlet oxygen ¹O₂. In the Reply it is shown that several arguments of the Comment are based on the incorrect statements. The current interpretation of the nature of the red shift and bandwidth of the luminescence of singlet oxygen governed by interaction with the environment is considered. It is shown that the characteristics of NIR luminescence (rather large red shift and bandwidth as compared with the literature data for the luminescence of ¹O₂ in solutions) observed in experiments by Demyanenko et al. are in a qualitative agreement with expected tendencies. All the arguments of the Comment are considered in detail and extended reply is given.