The photoelectron spectra of thiocarbonyl fluoride and thiocarbonyl chloride

Abstract

The photoelectron spectra of thiocarbonyl fluoride and thiocarbonyl chloride have been measured over the range 6 to 21 eV. Many of the bands observed have associated vibrational structure which can be correlated with the known vibration frequencies of the parent molecules. Ionization potentials have been assigned to molecular orbitals which are connected with lone pair electrons on the halogen or sulphur atoms, the C=S π orbitals, and σ orbitals. The values of some of these ionization potentials have been considered in relation to those of corresponding orbitals of carbonyl halides, formaldehyde and thioformaldehyde. Some calculations have been made on the changes of geometry occurring on ionization, using the intensity distribution of the Franck-Condon pattern of some of the bands.

Ion energetics measurements :

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