Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (1): 23-31.doi: 10.3866/PKU.WHXB201410311


Electronic Structure and Photoionization Dissociation Process of FC(O)SNCO

ZHAO Chun-Hong1,2, TONG Sheng-Rui1, GE Mao-Fa1, SUN Zheng2   

  1. 1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China;
    2. College of Chemistry and Materials Sciences, Hebei Normal University, Shijiazhuang 050024, P. R. China
  • Received:2014-09-03 Revised:2014-10-30 Published:2014-12-25
  • Contact: TONG Sheng-Rui, SUN Zheng;
  • Supported by:

    The project was supported by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (XDB05010400), National Natural Science Foundation of China (41105085, 21073051), and Natural Science Foundation of Hebei Province, China (B2010000368)


(Fluorocarbonyl) sulfenyl isocyanate (FC(O)SNCO) contains ―C(O)S― and ―NCO groups, so has an interesting electronic and molecular structure. FC(O)SNCO was prepared by the metathesis of FC(O)SCl and AgNCO. HeI photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and theoretical calculations were used to study the molecular and electronic structure of FC(O)SNCO. The experimental, theoretical calculations, and NBO results indicated the most stable conformer of FC(O)SNCO. In addition to the outer-valence Green's function calculation, the PES spectrumwas assigned fromanalogous studies of similar molecules. The syn-syn non-planar conformer (δFCSN=180°) with C1 symmetry was favored by the neutral molecule, and changed to the syn-syn planar structure with Cs symmetry after ionization. The experimental first vertical ionization potential mainly fromthe S lone pair orbital was 10.33 eV. The second to sixth ionization potentials of FC(O)SNCO were 12.44, 13.23, 13.77, 14.78, and 15.99 eV, respectively, and were also assigned. The FC(O)+, SN+, FC(O)SN+, SNCO+, C(O)SNCO+, and FC(O)SNCO peaks were observed in the PIMS spectrum, the highest intensity of which was FC(O)SNCO. The PIMS data were analyzed based on the PES and theoretical results. Possible ionization and dissociation processes are discussed.

Key words: Structure, HeI photoelectron spectroscopy, Photoionization mass spectroscopy, Theoretical calculation, Ionization and dissociation processes