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Photodissociation of acryloyl chloride in the gas phase

Photodissociation of acryloyl chloride in the gas phase
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摘要 The 193 nm photodissociation dynamics of CH2CHCOC1 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 (v ≤ 5), HC1 (v ≤ 6), and C2H2 were observed and two photodissociation channels, the C-C1 fission channel and the HC1 elimina- tion channel have been identified. The vibrational and rotational state distributions of the photofragments CO and HC1 have been acquired by analyzing their fully rotationally resolved v→ v- 1 rovibrational progressions in the emission spectra, from which it has been firmly established that the mechanism involves production of HC1 via the four-center molecular elimination of CH2CHCOC1 after its internal conversion from the S1 state to the So state. In addition to the dominant C--C1 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 CH2CHCOC1 as manifested by the considerable yield of HC1. The 193 nm photodissociation dynamics of CH2 CHCOCl 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 (≤ 5),HCl (≤ 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 v→v-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 CH2 CHCOCl 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 CH2 CHCOCl as manifested by the considerable yield of HCl.
出处 《Science China Chemistry》 SCIE EI CAS 2012年第3期359-367,共9页 中国科学(化学英文版)
基金 supported by the National Natural Science Foundation of China (20733005 &20973179)
关键词 TR-FTIR PHOTODISSOCIATION vibrational and rotational state distribution four-center elimination internal conversion 光解动力学 气相 丙烯酰氯 红外发射光谱 TR-FTIR 解离通道 振动激发 傅立叶变换
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