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Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer

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Abstract

A study of the atmospheric photochemical reaction of CF3 radical with CO and O2 was performed by using a homemade ultraviolet photoelectron spectrometer-photoionization mass spectrometer (PES-PIMS). The electronic structures and mechanism of ionization and dissociation of CF3OC(O)OOC(O)-OCF3 were investigated. It was indicated that the two bands on the photoelectron spectrum of CF3OC(O)OOC(O)OCF3 are the result of ionization of an electron from a lone pair of oxygen and a fluorine lone pair of CF3 group. The outermost electrons reside in the oxygen lone pair. The experimental and theoretical first vertical ionization energy is 13.21 and 13.178 eV, respectively, with the PES and OVGF method. They are in good agreement. The photo ionization and dissociation processes were discussed with the help of theoretical calculations and PES-PIMS experiment. After ionization, the parent ions prefer the dissociation of the C—O bond and giving the fragments CF3OCO+ and CF +3 . It demonstrated that the ultraviolet photoelectron and photoionization mass spectrometer could be applied widely in the study of atmospheric photochemical reaction.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100080, China

    Li Yao, Lin Du, Shi Yin & MaoFa Ge

  2. Graduate University of Chinese Academy of Sciences, Beijing, 100080, China

    Li Yao, Lin Du & Shi Yin

Authors
  1. Li Yao
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  2. Lin Du
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  3. Shi Yin
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  4. MaoFa Ge
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Correspondence to MaoFa Ge.

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Supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (Grant No. KZCX2-YW-205), Hundred Talents Fund, 973 Program of Ministry of Science and Technology of China (Grant No. 2006CB403701) and the National Natural Science Foundation of China (Grant Nos. 20577052, 20673123)

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Yao, L., Du, L., Yin, S. et al. Study on the atmospheric photochemical reaction of CF3 radicals using ultraviolet photoelectron and photoionization mass spectrometer. Sci. China Ser. B-Chem. 51, 316–321 (2008). https://doi.org/10.1007/s11426-007-0105-x

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  • DOI: https://doi.org/10.1007/s11426-007-0105-x

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