The XPS peak structure of condensed aromatic anhydrides and imides

Photoelectron spectra of aromatic anhydrides and imides like PTCDA (perylene-tetracarboxylic dianhydride), PTCDI (perylene-tetracarboxylic diimide), and NDCA (naphthalene-dicarboxylic anhydride) on smooth single crystal surfaces show complex double peak structures in both the O1s and the anhydride C1s range. The peak intensity ratios cannot be simply explained by different chemical states of the atoms but are strongly influenced by intense shake-up satellites. Semiempirical SDCI calculations can quantitatively reproduce the experimental spectra of multilayers, provided that not only intramolecular but also intermolecular shake-up excitations are taken into account. These calculations give further insight into the process of electronic charge transfers in large organic molecules and molecular films. A variation of the molecular structure by reducing the size of the aromatic part (NDCA instead of PTCDA) or by using different functional groups (PTCDI instead of PTCDA) leads to a reduced donor/acceptor strength and hence to drastically reduced satellite intensities.