Photodissociation of acryloyl chloride in the gas phase
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The 193 nm photodissociation dynamics of CH2CHCOCl in the gas phase has been examined with the technique of time-resolved Fourier transform infrared emission (TR-FTIR) spectroscopy. Vibrationally excited photofragments of CO (ν ⩽ 5), HCl (ν ⩽ 6), and C2H2 were observed and two photodissociation channels, the C-Cl fission channel and the HCl elimination channel have been identified. The vibrational and rotational state distributions of the photofragments CO and HCl have been acquired by analyzing their fully rotationally resolved ν→ν−1 rovibrational progressions in the emission spectra, from which it has been firmly established that the mechanism involves production of HCl via the four-center molecular elimination of CH2CHCOCl after its internal conversion from the S1 state to the S0 state. In addition to the dominant C-Cl bond fission along the excited S1 state, the S1→S0 internal conversion has also been found to play an important role in the gas phase photolysis of CH2CHCOCl as manifested by the considerable yield of HCl.
KeywordsTR-FTIR photodissociation vibrational and rotational state distribution four-center elimination internal conversion
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- 4.Brocksom TJ, Coelho F, Depres JP, Greene AE, de Lima MEF, Hamelin O, Hartmann B, Kanazawa AM, Wang YY. First comprehensive bakkane approach: Stereoselective and efficient dichloroketene-based total syntheses of (±)- and (−)-9-acetoxyfukinanolide, (±)- and (+)-bakkenolide A, (−)-bakkenolides III, B, C, H, L, V, and X, (±)- and (−)-homogynolide A, (±)-homogynolide B, and (±)-palmosalide C. J Am Chem Soc, 2002, 124: 15313–15325CrossRefGoogle Scholar
- 20.Lin S-R, Lin S-C., Lee Y-C, Chou I-C, Chen I-C, Lee Y-P. Three-center versus four-center HCl-elimination in photolysis of vinyl chloride at 193 nm: Bimodal rotational distribution of HCl (ν ⩽7) detected with time-resolved Fourier-transform spectroscopy. J Chem Phys, 2001, 114: 160–168CrossRefGoogle Scholar