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Abstract

The construction of a high resolution photoelectron spectrometer (15 mV) has enabled detailed study of molecular ionization potentials. A brief account of historical and experimental developments is described. Spectra of some "divalent" sulphur-containing compounds have been recorded, and the effect of different alkyl groups on the sulphur "non-bonding" orbital is discussed. 3d orbital participation in some thionyl and sulphury1 halides (SOCl₂, SO₂Cl₂, SOF₂ and SO₂F₂) is considered in the interpretation of the spectra. The inductive and resonance effects in some dibromoethylenes is discussed, and the assignment of bromine "lone pair" orbitals is made. Evidence of (P → d) π bonding in some halisalanes SiH₃X (X = F, Cl, Br) and SiH[sub 4-n]X[sub n] (X = Cl) is discussed, and compared with analogous carbon containing compounds. CNDO/2 and INDO semi-empirical calculations are used in order to assist the assignment of the PE spectra.