Electrical conduction in polyethylene: The role of positive charge and the formation of positive packets

A model for positive hole transport in polyethylene is developed which takes particular account of the crystalline-amorphous morphology of the polymer. The significant feature is the employment of super-exchange quantum mechanical tunneling to explain hole transport through the amorphous phase. The consequence is that the hole mobility exhibits a maximum as a function of the electric field, a manifestation of the inverse Marcus effect. It is shown that this feature accounts for the majority of the reported high-field hole transport effects in polyethylene, including packet formation.