The coherent scattering function of the reptation model: simulations compared to theory

TL;DR

This study uses Monte Carlo simulations to measure the coherent structure function of polymer chains in a lattice, comparing results to various theoretical models, and finds the full reptation model provides the best fit across different conditions.

Contribution

The paper provides a comprehensive simulation comparison of the reptation model with primitive and Rouse models, validating the full reptation model's accuracy in describing chain dynamics.

Findings

Primitive chain model fits data for t > 20 T_2 with T_3 as a fit parameter.

Rouse in a tube model fails to match simulation results.

Full reptation model accurately describes the data across wave vectors and times.

Abstract

We present results of Monte Carlo simulations measuring the coherent structure function of a chain moving through an ordered lattice of fixed topological obstacles. Our computer experiments use chains up to 320 beads and cover a large range of wave vectors and a time range exceeding the reptation time. -- We compare our results (i) to the predictions of the primitive chain model, (ii) to an approximate form resulting from Rouse motion in a coiled tube, and (iii) to our recent evaluation of the full reptation model. (i) The primitive chain model can fit the data for times t \gt 20 T_2, where T_2 is the Rouse time of the chain. Besides some phenomenological amplitude factor this fit involves the reptation time T_3 as a second fit parameter. For the chain lengths measured, the asymptotic behavior T_3 ~ N^3 is not attained. (ii) The model of Rouse motion in a tube, which we have criticized before on theoretical grounds, is shown to fail also on the purely phenomenological level. (iii) Our evaluation of the full reptation model yields an excellent fit to the data for both total chains and internal pieces and for all wave vectors and all times, provided specific micro-structure effects of the MC-dynamics are negligible. Such micro-structure effects show up for wave vectors of the order of the inverse segment size. For the dynamics of the total chain our data analysis based on the full reptation model shows the importance of tube length fluctuations. Universal (Rouse-type) internal relaxation is unimportant. It can be observed only in the form of the diffusive motion of a short central subchain in the tube. -- Finally we present a fit formula which in a large range of wave vectors and chain lengths reproduces the numerical results of our theory for the scattering from the total chain.