FC(O)SNCO的电子结构和光电离解离过程

doi:10.3866/PKU.WHXB201410311

Abstract

Abstract:

(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 (δ_FCSN=180°) with C₁ symmetry was favored by the neutral molecule, and changed to the syn-syn planar structure with C_s 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

ZHAO Chun-Hong, TONG Sheng-Rui, GE Mao-Fa, SUN Zheng. Electronic Structure and Photoionization Dissociation Process of FC(O)SNCO[J]. Acta Phys. -Chim. Sin. 2015, 31(1), 23-31. doi: 10.3866/PKU.WHXB201410311

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

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