Polymer chain dynamics: evidence of nonexponential mode relaxation using thermally stimulated depolarization current techniques.

The slowest (p=1) mode relaxation of several polyisoprenes has been experimentally isolated by thermally stimulated depolarization current techniques. Close to the glass transition the p=1 mode deviates from the exponential behavior assumed by Rouse and tube-reptation theories. This effect is found to be a consequence of the closeness of τ_{p=1} and α-relaxation time scales. The scenario resembles that of broadened fast component dynamics in polymer blends with high dynamic asymmetry and suggests a possible general interpretation in terms of the effect of local density fluctuations (α relaxation) on chain dynamics.