ESCA applied to polymers. XXXI. A theoretical investigation of molecular core binding and relaxation energies in a series of prototype systems for nitrogen and oxygen functionalities in polymers

Abstract

Nonempirical LCAO MO SCF computations (in the ΔSCF formalism) were performed on the ground and core‐hole states of a range of nitrogen‐containing model systems which encompass most of the common functionalities of interest in the study of polymers. The data complement those previously presented on oxygen functionalities and show that for specific functionalities (e.g. nitrate esters and nitriles) substituent effects can be substantially different than normally anticipated on the basis of a simple additivity model. A comparison was drawn in appropriate cases with experimental data on simple model systems and polymers.