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Toward the spectrum of free polyethylene: linear alkanes studied by carbon 1s photoelectron spectroscopy and theory.

Trends in carbon 1s ionization energies for the linear alkanes have been investigated using third-generation synchrotron radiation. The study comprises CH(4), C(2)H(6), C(3)H(8), C(4)H(10), C(5)H(12), C(6)H(14), and C(8)H(18). Both inter- and intramolecular shifts in ionization energy have been determined from gas-phase spectra and ab initio calculations. The shifts are decomposed into initial-state and final-state contributions and are shown to relate to the fundamental chemical properties of group electronegativity and polarizability. By extrapolation, we predict C1s spectra of larger n-alkanes, converging toward isolated strands of polyethylene.