Molecular Dynamics Study of Relaxation Modes of a Single Polymer Chain

Abstract

Relaxation modes and rates of a single polymer chainwith the excluded volume interaction is studiedby molecular dynamics simulations.The variational method for the estimation of the relaxation modes and ratesproposed by Takano and Miyashita[J. Phys. Soc. Jpn. 64 (1995) 3688] is generalized to cases where the detailed balance condition is not satisfiedand applied to the results of the present simulations.The relaxation modes and rates estimated by the generalized methoddescribe the behaviors of the autocorrelation functionsof relative velocities and relative positions of the segments well.For a polymer chain with N segments, the behavior of the pth slowest relaxation rate λ_pwith p/N << 1 is consistent with the theoretical predictionλ_p ∝ (p/N)^{2ν + 1}, where ν isthe exponent for the size of a polymer chain in good solvent.