Photochemistry and Photophysics of n-Butanal, 3-Methylbutanal, and 3,3-Dimethylbutanal: Experimental and Theoretical Study

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2012-06, Vol.116 (24), p.5830-5839
• Main Authors: Tadić, Jovan M, Moortgat, Geert K, Bera, Partha P, Loewenstein, Max, Yates, Emma L, Lee, Timothy J
• Format: Article
• Language: English
• Subjects: Channels; Ethene; Excitation; Fluorescence; Photolysis; Photooxidation; Physical chemistry; Radicals
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp208665v

Dilute mixtures of n-butanal, 3-methylbutanal, and 3,3-dimethylbutanal in synthetic air, different N2/O2 mixtures, and pure nitrogen (up to 100 ppm) were photolyzed with fluorescent UV lamps (275–380 nm) at 298 K. The main photooxidation products were ethene (n-butanal), propene (3-methylbutanal) or i-butene (3,3-dimethylbutanal), CO, vinylalcohol, and ethanal. The photolysis rates and the absolute quantum yields were found to be dependent on the total pressure of synthetic air but not of nitrogen. At 100 Torr, the total quantum yield Φ100 = 0.45 ± 0.01 and 0.49 ± 0.07, whereas at 700 Torr, Φ700 = 0.31 ± 0.01 and 0.36 ± 0.03 for 3-methylbutanal and 3,3-dimethybutanal, respectively. Quantum yield values for n-butanal were reported earlier by Tadić et al. (J. Photochem. Photobiol. A 2001 143, 169–179) to be Φ100 = 0.48 ± 0.02 and Φ700 = 0.32 ± 0.01. Two decomposition channels were identified: the radical channel RCHO → R + HCO (Norrish type I) and the molecular channel CH3CH(CH3)CH2CHO → CH2CHCH3 + CH2CHOH or CH3C(CH3)2CH2CHO → CHC(CH3)CH3 + CH2CHOH, (Norrish type II) having the absolute quantum yields of 0.123 and 0.119 for 3-methybutanal and 0.071 and 0.199 for 3,3-dimethylbutanal at 700 Torr of synthetic air. The product ethenol CH2CHOH tautomerizes to ethanal. We have performed ab initio and density functional quantum (DFT) chemical computations of both type I and type II processes starting from the singlet and triplet excited states. We conclude that the Norrish type I dissociation produces radicals from both singlet and triplet excited states, while Norrish type II dissociation is a two-step process starting from the triplet excited state, but is a concerted process from the singlet state.