Interference and diffraction in photoelectron spectra

Highlights: • High energy oscillations in the photoionization cross sections. • Interference and diffraction in molecular photoionization. • Non-stoichiometric cross sections. • Core and valence photoionization cross sections in haloacetylenes. - Abstract: Theoretical calculations are employed to disentangle the effect due to coherent emission from equivalent centres and diffraction from neighbouring inequivalent atoms in core and valence photoelectron spectra. The molecules investigated are mono and disubstituted fluoro and iodo acetylenes, compared to the simple acetylene system. The two effects appear well separated and additive in the core region, with diffraction giving oscillations of smaller amplitude, shorter period, and more strongly damped. Their interplay is more complex in the valence region giving rise to irregular patterns which, although rich in information, are more difficult to analyze. It is shown that the use of an external standard molecule can be profitably used to reveal diffraction patterns in the case where no internal ratio is available