Modeling the collective relaxation time of glass-forming polymers at intermediate length scales: Application to polyisobutylene

Abstract

In a recent paper [V. N. Novikov, K. S. Schweizer, and A. P. Sokolov, J. Chem. Phys. 138, 164508 (2013)] a simple analytical ansatz has been proposed to describe the momentum transfer (Q) dependence of the collective relaxation time of glass-forming systems in a wide Q-range covering the region of the first maximum of the static structure factor S(Q) and the so-called intermediate length scale regime. In this work we have generalized this model in order to deal with glass-forming systems where the atomic diffusive processes are sub-linear in nature. This is for instance the case of glass-forming polymers. The generalized expression considers a sub-linear jump-diffusion model and reduces to the expression previously proposed for normal diffusion. The generalized ansatz has been applied to the experimental results of the Q- and temperature-dependence of polyisobutylene (PIB), which were previously published. To reduce the number of free parameters of the model to only one, we have taken advantage of atomistic molecular dynamics simulations of PIB properly validated by neutron scattering results. The model perfectly describes the experimental results capturing both, Q- and temperature-dependences. Moreover, the model also reproduces the experimental Q-dependence of the effective activation energy of the collective relaxation time in the temperature range of observation. This non-trivial result gives additional support to the way the crossover between two different relaxation mechanisms of density fluctuations is formulated in the model.