An internal configuration bias sampling method for dense polymer systems

A new internal configuration bias (ICB) scheme for Monte Carlo (MC) sampling of any number of internal degrees of freedom in chain molecules with arbitrary fixed bond lengths and angles is proposed, extending recent methods restricted to lattice chains, freely jointed chains or short segments. The move is described pictorially for the case of a linear chain; the method may also be readily generalised to branched chains or networks. Its application to a 'phantom' hexadecane backbone with no interatomic potential confirms that it satisfies detail balance. Its application in a strategy for atomistic simulation of bulk polymeric systems is depicted. Unlike previous polymer MC schemes ICB is not dependent on the presence of chain ends, making it potentially highly suitable for the kinds of dense, entangled, high molecular weight and crosslinked systems relevant to applications in the polymer industry