title: Effect of bending and torsion rigidity on self-diffusion in polymer melts: a molecular-dynamics study.
abstract: 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 proportional to N(-nu) with nu=1 for N<Ne (Rouse regime) and with nu=2 for N>Ne (reptation regime), Ne being the entanglement length. Our simulations, at constant temperature and density, up to N=250 reveal that, as the chain rigidity increases, the exponent nu gradually increases towards nu=2.0 for N<Ne and nu=2.2 for N>Ne. The value of Ne 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.
authors.affiliation: Materials Science Centre, University of Groningen, The Netherlands. m.i.bulacu-cioceanu@rug.nl
authors.forename: Monica
authors.initials: M
authors.lastname: Bulacu
authors.forename: Erik
authors.initials: E
authors.lastname: van der Giessen
mesh_terms: D001704:Biopolymers / Q000737:chemistry*; D003198:Computer Simulation; D004058:Diffusion; D004548:Elasticity; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D044367:Phase Transition; D012399:Rotation; D013314:Stress, Mechanical; D019415:Torque; D044366:Transition Temperature
chemical_list: D001704:Biopolymers