The ultra-violet photoelectron spectra of gas-phase and condensed bismuth halides and antimony trifluoride

Abstract

He(Iα) and He(IIα) photoelectron spectra of BiX₃(X = F, Cl, Br, and I) and of SbF₃ molecules have been recorded and analysed on the basis of empirical considerations such as He(I)–He(II) intensity variations, the relative intensities of bands, and correlations with the spectra of related compounds for which assignments are established. Spin-orbit interaction was observed in systems corresponding to ionization from both halogen lone pair orbitals and BiX bonding orbitals. Photoelectron spectra of condensed BiX₃ solids are also reported and shown to correspond closely with the molecular spectra, indicating a close relationship between the solid state and molecular electronic structure.