A theoretical investigation of molecular core binding and relaxation energies in a series of oxygen‐containing organic molecules of interest in the study of surface oxidation of polymers

Abstract

AbstractNonempirical LCAO MO SCF computations (in the ΔSCF 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 Cls and Ols core levels. A sound basis is therefore provided for the discussion of relative core binding energies (Cls and Ols) 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. Cls 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 Ols levels a similar but less straightforward situation exists. The relaxation energies associated with both Cls and Ols core ionization follow a dependence on the binding energy for a given structural type.