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

► X-ray photoelectron spectra (XPS) of polymers: C(1s) binding energy (BE). ► Quantum chemical investigation of XPS shifts of poly(vinyltrifluoroacetate). ► BEs depend on details of charge distribution of the entire molecule. ► Typical nearest-neighbor analysis of XPS is not sufficient. ► Setting lowest C(1s) BE to 285.0 eV for functionalized polyvinyls is questionable.