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Ab initio calculations for XPS chemical shifts of poly(vinyl-trifluoroacetate) using trimer models

: Kröner, D.; Ehlert, C.; Saalfrank, P.; Holländer, A.


Surface Science 605 (2011), No.15-16, pp.1516-1524
ISSN: 0039-6028
Journal Article
Fraunhofer IAP ()

X-ray photoelectron spectra (XPS) of the polymer poly(vinyl-trifluoroacetate) show C(1s) binding energy shifts which are unusual because they are influenced by atoms which are several bonds away from the probed atom. In this work, the influence of the trifluoroacetate substituent on the 1s ionization potential of the carbon atoms of the polyethylene chain is investigated theoretically using mono-substituted, diad and triad models of trimers representing the polymer. Carbon 1s ionization energies are calculated by the Hartree-Fock theory employing Koopmans' theorem. The influence of the configuration and conformation of the functional groups as well as the degree of substitution are found to be important determinants of XPS spectra. It is further found that the 1s binding energy correlates in a linear fashion, with the total electrostatic potential at the position of the probe atom, and depends not only on nearest neighbor effects. This may have implications for the interpretation of high-resolution XP spectra.