Molecular orbital simulations on electron-induced degradation of perfluoropolyethers with several types of segments

Semi-empirical molecular orbital simulations on electron-induced degradation of perfluoropolyethers (PFPEs) with several types of segments, such as methylene oxide, ethylene oxide, ethylene oxide-methylene oxide, linear and branched propylene oxide, were carried out. The calculated heat of formation indicated that the anion radical states of these species had lower energy levels compared to neutral states. The paper postulates that electron attachment to PFPE easily occurs on electron-rich surfaces, The anion radical was supposed to decompose to an anion and a neutral radical, while the cation radical was expected to degrade to a cation and a neutral radical. The formation of carbonyl difluoride was simulated in the case of the decomposition of perfluoropropylene oxide cation radical. Copyright (C) 1996 Elsevier Science Ltd