High-order sampling schemes for path integrals and Gaussian chain simulations of polymers

Abstract

In this work, we demonstrate that path-integral schemes, derived in the context of many-body quantum systems, benefit the simulation of Gaussian chains representing polymers. Specifically, we show how to decrease discretization corrections with little extra computation from the usual O(1/P-2) to O(1/P-4), where P is the number of beads representing the chains. As a consequence, high-order integrators necessitate much smaller P than those commonly used. Particular emphasis is placed on the questions of how to maintain this rate of convergence for open polymers and for polymers confined by a hard wall as well as how to ensure efficient sampling. The advantages of the high-order sampling schemes are illustrated by studying the surface tension of a polymer melt and the interface tension in a binary homopolymers blend. (C) 2015 AIP Publishing LLC.