Photoelektronen-Spektren und Moleküleigenschaften. 132 [1, 2]. Trifluormethylsulfan und Derivate F3CSX (X CF3, Cl,Br, I) |
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Authors: | Hans Bock Matthias Kremer Bahman Solouki Rolf Minkwitz |
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Abstract: | Photoelectron Spectra and Molecular Properties. 132. Trifluoromethylsulfane and Derivatives F3CSX (X ? CF3, Cl, Br, I) The He(I) photoelectron spectra of trifluoromethylsulfane F3CSH and its derivatives F3CSX (X ? CF3, Cl, Br, I) are assigned by Koopmans' correlations, IE = ?ε, with MNDO eigenvalues, by radical cation state comparison and based on resolved vibrational fine structures, which can' be discussed by MNDO FORCE calculations. The spin/orbit splitting in F3CSI can be approximated by additional ITEREX-85 calculations. Gasphase thermolysis of the trifluoromethylhalogensulfanes F3CSX at 10?4 mbar yields decomposition temperatures, which decrease from X ? Cl to I, and as fragmentation products of presumably radical intermediates, in addition to the respective halogens X2 and F2C?S, also F3CX as well as S2 and CS2 (X ?Cl, Br) are PE spectroscopically detected. |
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Keywords: | Trifluoromethylsulfane and derivatives Photoelectron spectra MNDO calculations Thermal decomposition |
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