Accelerated equilibration of polymer melts by time-coarse-graining

Abstract

An effective‐potential approach is presented for improving sampling efficiency in simulations of atomistically detailed models of dense long‐chain liquids. The motion of atoms on short‐time scales is described as rapid fluctuations about the slowly moving mean conformations of the chain molecules. The distribution of these fluctuations is approximated by that of isotropic elastic motion. The interactions between nonbonded pairs of atoms are preaveraged over this distribution and a much softer, effective interaction is obtained, allowing a correspondingly faster exploration of configuration space. The approximate sampling scheme is then tested on two model systems of united‐atom liquid hydrocarbons—a melt of twenty C24 chains and one of ten C71 chains. In the C24 melt, where a comparison with fully equilibrated samples from rigorous algorithms is possible, the preaveraging is shown to produce an improvement in sampling efficiency of up to an order of magnitude at the expense of only a moderate loss in accuracy. The method is then applied to the C71 melt, where currently available, rigorous sampling algorithms fail to produce thorough equilibration. Also in this case, the preaveraging method proves to significantly enhance the sampling speed while producing satisfactory distributions of observables.