Structure and Electron Configuration of Imidazole-2-carboxaldehyde and Its Excited Triplet: Resonance Raman and Transient Absorption Spectroscopy and DFT Calculation Investigations

Imidazole-2-carboxaldehyde (IC) can be generated in atmospheric waters and absorbs solar radiation in the near UV region to produce its excited triplet state (3IC), which contributes to the formation of a secondary organic aerosol (SOA). The photoreactivity of IC is significantly influenced by its surroundings, such as water and acidic environment, because IC is capable of transforming into gem-diol under above conditions. Meanwhile, the electron configuration of 3IC is critical in elucidating the reaction mechanism of 3IC with other anthropogenic and biogenic volatile organic compounds (VOCs). In this study, steady-state and time-resolved resonance Raman as well as transient absorption spectroscopic experiments were conducted to provide vibrational and kinetic information on IC and 3IC in the presence of water and acid conditions. Using density functional theory (DFT) calculations, the H-bonding at the carbonyl O was confirmed and the hydrated structure of IC and 3IC was determined. 1,4-Cyclohexadiene is a good hydrogen donor, and it has a second-order rate constant of ∼107 M–1 s–1 toward 3IC. The results of CASSCF calculations suggest that the hydrogen abstraction may involve the transition from the ππ* to nπ* triplet state via the surface-crossing point.