Characterization of the "simple-liquid" state in a polymeric system: Coherent and incoherent scattering functions

By means of time-of-flight neutron scattering, we have characterized the dynamic structure factor and the hydrogen motions of polyethylene above its melting point. As signatures of simple-liquid dynamics, we observe that (i) in the explored dynamic window, the intermediate scattering functions display a single-step decay, without reminiscence of cage effects, and (ii) the structural relaxation as observed at the intermolecular structure factor peak shows a weak temperature dependence, indicating a low degree of interchain cooperativity. However, stretched functional forms are observed for all length scales and temperatures investigated. An apparent direct crossover from the microscopic regime to Rouse-like dynamics suggests an essential role of connectivity in the observed stretching. Finally, while at momentum-transfer values above the structure factor peak the relation between coherent and incoherent characteristic times is reasonably described by the de Gennes narrowing, at larger length scales it is not reproduced by any existing approach.