Effect of bending and torsion rigidity on self-diffusion in polymer melts: A molecular-dynamics study.

Extensive molecular-dynamics simulations have been performed to study the effect of chain conformational rigidity, controlled by bending and torsion potentials, on self-diffusion in polymer melts. The polymer model employs a novel torsion potential that avoids computational singularities without the need to impose rigid constraints on the bending angles. Two power laws are traditionally used to characterize the dependence of the self-diffusion coefficient on polymer length: D∝N^-ν with ν=1 for N<N_e (Rouse regime) and with ν=2 for N>N_e (reptation regime), N_e being the entanglement length. Our simulations, at constant temperature and density, up to N=250 reveal that, as the chain rigidity increases, the exponent ν gradually increases towards ν=2.0 for N<N_e and ν=2.2 for N>N_e. The value of N_e is slightly increased from 70 for flexible chains, up to the point where the crossover becomes undefined. This behavior is confirmed also by an analysis of the bead mean-square displacement. Subsequent investigations of the Rouse modes, dynamical structure factor, and chain trajectories indicate that the pre-reptation regime, for short stiff chains, is a modified Rouse regime rather than reptation. [ABSTRACT FROM AUTHOR]