Nonempirical LCAO MO SCF computations (in the DELTA SCF formalism) have been carried out of binding energies and relaxation energies for an extensive series of oxygen-containing organic systems encompassing most of the common functionalities. The molecules for which experimental data are available for comparison demonstrate the adequacy of the treatment for describing the relative binding energies for both the C//1//s and O//1//s core levels. A sound basis is therefore provided for the discussion of relative core binding energies (C//1//s and O//1//s) for functionalities for which experimental data are not available, that is, hydroperoxides, peroxides, peroxyacids, and peroxyesters, a knowledge of which is essential for investigations of the surface oxidation of polymers by means of ESCA. C//1//s shifts are discussed in terms of primary and secondary substituent effects of oxygen, which greatly simplify the analysis of complex unresolved spectra, whereas for the O//1//s levels a similar but less straightforward situation exists. The relaxation energies associated with both C//1//s and O//1//s core ionization follow a dependence on the binding energy for a given structural type.
