First-principles calculations are used to investigate the electronic properties of the surfaces of polyethylene. The calculations support the experimental evidence of a negative electron affinity, with calculated values of - 0.17 eV and - 0.10 eV for surfaces with chains perpendicular and parallel to the surface normal, respectively. Both surfaces exhibit a surface state with binding energy - 1.2 +/- 0.5 eV with respect to the bulk polyethylene conduction band minimum. Implications of these findings on spectroscopy, as well as on the transport and aging properties of polyethylene for high-voltage applications, are discussed.
