Equilibrium and non-equilibrium molecular dynamics approaches for the linear viscoelasticity of polymer melts

Abstract

Viscoelastic properties of polymer melts are particularly challenging to compute due to the intrinsic stress fluctuations in molecular dynamics (MD). We compared equilibrium and non-equilibrium MD approaches for extracting the storage (G′) and loss moduli (G″) over a wide frequency range from a bead-spring chain model in both unentangled and entangled regimes. We found that, with properly chosen data processing and noise reduction procedures, different methods render quantitatively equivalent results. In equilibrium MD (EMD), applying the Green−Kubo relation with a multi-tau correlator method for noise filtering generates smooth stress relaxation modulus profiles from which accurate G′ and G″ can be obtained. For unentangled chains, combining the Rouse model with a short-time correction provides a convenient option that circumvents the stress fluctuation challenge altogether. For non-equilibrium MD (NEMD), we found that combining a stress pre-averaging treatment with discrete Fourier transform analysis reliably computes G′ and G″ with a much shorter simulation length than previously reported. Comparing the efficiency and statistical accuracy of these methods, we concluded that EMD is both reliable and efficient, and is suitable when the whole spectrum of linear viscoelastic properties is desired, whereas NEMD offers flexibility only when some frequency ranges are of interest.