The He(I) photoelectron spectroscopy of heavy group IV-VI diatomics

The He(I) photoelectron spectra of the Group IV-VI diatomics GeO, GeS, GeSe, GeTe, SnS, SnSe, and SnTe are presented. The outermost valence structure of these molecules is similar to that observed in the lighter series CO, CS, etc. of this valence isoelectronic group; in each case a relatively sharp peak is assigned to ionization from the nominally non-bonding 3σ orbital and a broader band to ionization from the bonding 1π orbital. At higher binding energies the spectra exhibit several peaks where only a single peak is expected, from the (2σ)^-1 hole state. This structure is assigned to correlation peaks resulting from configuration interaction among hole states of ²Σ⁺ (Ω = 1 2) symmetry. Semi-empirical CNDO-MO calculations have been performed for these molecules, and the results are used to interpret the observed trends. In addition, a simple molecular orbital model is employed to estimate the importance of spin-orbit coupling in the valence electronic structure of the heavy IV-VI ions.