Linear Viscoelasticity of Semidilute Unentangled Flexible Polymer Solutions

Abstract The linear viscoelastic response of flexible polymer solutions in the dilute and semidilute unentangled regimes is investigated using Brownian dynamics simulations. The relaxation modulus and dynamic moduli are computed over a wide range of concentrations and chain discretizations for both θ and good solvents. In the dilute limit, the simulations recover Zimm-like behavior with solvent-quality-dependent power-law scaling in the intermediate-time and -frequency regimes, while in the semidilute unentangled regime, a systematic crossover to Rouse-like dynamics is observed with increasing concentration due to the screening of excluded volume and hydrodynamic interactions. Comparison with experimental measurements shows excellent agreement for the storage modulus across both concentration regimes and for the loss modulus at low and intermediate frequencies, with deviations at high frequencies due to finite-chain discretization effects. Systematic accounting for these finite-chain-length effects using successive fine-graining enables quantitative prediction of the loss modulus in the infinite-chain-length limit.