Simulating dynamic crossover behavior of semiflexible linear polymers in solution and in the melt

Abstract

We present a molecular dynamics study of the dynamic scaling behavior of linear polymers in solution and in the melt when their character changes from fully flexible to semiflexible. The stiffness of the chains is determined by a bending potential. It is shown that the relaxation times tau(p) characterizing the internal dynamics of the polymer chains as well as the mean square mode amplitudes <chi(p)(2)> exhibit a clear crossover from Rouse to bending modes with increasing mode number p. For small mode numbers p the well-known p(-2) Rouse behavior is observed, whereas large mode numbers exhibit the p(-4) scaling, typical of the bending modes of semiflexible chains. We study the extension and the onset of the region where the crossover from p(-2) to p(-4) behavior occurs. With increasing stiffness of the chains we observe a shift of the crossover domain to smaller p-values. We also investigate the effect of chain stiffness on the monomer dynamics, based on their mean square displacements. Finally, we compare our results to previous simulations, where the scaling behavior of semiflexible chains was studied and which were restricted to a smaller range of persistence lengths l(p) and p values.