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Additional info for Characterization of Metal and Polymer Surfaces. Volume 2: Polymer Surfaces
To complement the experimental studies, theoretical computations of shake up probabilities have been made within the sudden approximation employing the equivalent cores concept and a semi-empirical all valence electron SCF MO formalism. Within this framework, the calculation of shake up probabilities involves summation over weighted overlap terms involv ing the occupied and virtual orbitals involved in the transitions. For the parent polystyrene, the marked asymmetry of the satellite structure to the C ls levels strongly suggests that at least two transitions are involved.
Atom % values given here consider only the elements detected by ESCA. Normalization was used in order to eliminate the effect of changes in emission induced by variations in fracture topogra phy. This procedure also eliminated the effect of the increase in emission displayed by all elements after sputtering the sili cone polymers. Apparently a change in surface density or rough ness occurs. A rearrangement of a simplified expression for photo 58 Dwight E. Williams and Lawrence E. Davis Si—2 p C—1 s Fig.
90. The fact that an additive model applies to the experimental data but with a much larger dependence of intensity on n than predicted theoretically would strongly suggest that there are specific orient ation effects of the polymer chains in the surface regions sampled by ESCA. An alternative possibility is that the samples are contam inated with hydrocarbon. Such contamination would contribute to the C^s peak at 285 eV but not to the low energy satellite structure. Even if the extent of contamination were such as to produce the linear correlation found experimentally (which is most unlikely on the basis of the method of preparation)3k, on the basis of the likely escape depth dependence on kinetic energy for C^s levels employing Mg radiation such an explanation is untenable3.