Exciton self-trapping in bulk polyethylene

We studied theoretically the behavior of an injected electron-hole pair in crystalline polyethylene. Time-dependent adiabatic evolution by ab-initio molecular dynamics simulations show that the pair will become self-trapped in the perfect crystal, with a trapping energy of about 0.38 eV, with formation of a pair of trans-gauche conformational defects, three C$_2$H$_4$ units apart on the same chain. The electron is confined in the inter-chain pocket created by a local, 120$^\circ$ rotation of the chain between the two defects, while the hole resides on the chain and is much less bound. Despite the large energy stored in the trapped excitation, there does not appear to be a direct non-radiative channel for electron-hole recombination. This suggests that intrinsic self-trapping of electron-hole pairs inside the ideal quasi-crystalline fraction of PE might not be directly relevant for electrical damage in high-voltage cables.

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