40.81 eV photoelectron spectroscopy of the thallous halides

Photoelectron spectra (using 40.81 eV photons) of TlF, TlCl, TlBr and TlI are presented. Absolute binding energies of the outermost halogen np levels with respect to the vacuum level and the energy separations between the thallium 5d_5/2 level and the halogen np level are compared with the corresponding energies predicted using the Born model for ionic solids. The thallium ion ²D_5/2 and ²D_3/2 final states display a non-statistical branching ratio and this is explained in terms of the relative photoionization cross-sections of d_5/2 and d_3/2 electrons. Structure in the spectrum of TIF is interpreted in terms of molecular orbital-like states.