Correlated Molecular Structural Motions for Photoprotection after Deep-UV Irradiation

Exposure to ultraviolet (UV) light could cause photodamage to biomolecular systems and degrade optoelectronic devices. To mitigate such detrimental effects from the bottom up, we strategically select a photosensitive molecule pyranine and implement femtosecond electronic and Raman spectroscopies to elucidate its ultrafast photoprotection mechanisms in solution. Our results show that pyranine undergoes excited-state proton transfer in water, while this process is blocked in methanol regardless of excitation wavelengths (267, 400 nm). After 267 nm irradiation, the molecule relaxes from a higher lying electronic state into a lower lying singlet state with a <300 fs time constant, followed by solvation events. Transient Raman marker bands exhibit different patterns of intensity dynamics and frequency shift that elucidate the real-time interplay among conformational motions, photochemical reaction, and vibrational cooling after excitation. More energetic photons are revealed to selectively enhance certain rela...