Photoelectron spectroscopic studies of the silicon pseudohalides: relationship between geometrical and electronic structure

Abstract

The He I photoelectron spectra of the molecules (CH₃)_nY(NCX)_4–n(Y = C, Si and X = O, S and Se) have been recorded and analysed on the basis of ab initio Hartree–Fock SCF calculations. Optimized geometries for the molecules with n= 3 were obtained. The pseudolinear behaviour and its effect on the photoelectron spectra was investigated. The inclusion of correlation in the calculations is important to predict the geometry of these molecules correctly.