Interior segment regrowth configurational-bias algorithm for the efficient sampling and fast relaxation of coarse-grained polyethylene and polyoxyethylene melts on a high coordination lattice.

Abstract

We demonstrate the application of a modified form of the configurational-bias algorithm for the simulation of chain molecules on the second-nearest-neighbor-diamond lattice. Using polyethylene and poly(ethylene-oxide) as model systems we show that the present configurational-bias algorithm can increase the speed of the equilibration by at least a factor of 2-3 or more as compared to the previous method of using a combination of single-bead and pivot moves along with the Metropolis sampling scheme [N. Metropolis, A. W. Rosenbluth, M. N. Rosenbluth, A. H. Teller, and E. Teller, J. Chem. Phys. 21, 1087 (1953)]. The increase in the speed of the equilibration is found to be dependent on the interactions (i.e., the polymer being simulated) and the molecular weight of the chains. In addition, other factors not considered, such as the density, would also have a significant effect. The algorithm is an extension of the conventional configurational-bias method adapted to the regrowth of interior segments of chain molecules. Appropriate biasing probabilities for the trial moves as outlined by Jain and de Pablo for the configurational-bias scheme of chain ends, suitably modified for the interior segments, are utilized [T. S. Jain and J. J. de Pablo, in Simulation Methods for Polymers, edited by M. Kotelyanskii and D. N. Theodorou (Marcel Dekker, New York, 2004), pp. 223-255]. The biasing scheme satisfies the condition of detailed balance and produces efficient sampling with the correct equilibrium probability distribution of states. The method of interior regrowth overcomes the limitations of the original configurational-bias scheme and allows for the simulation of polymers of higher molecular weight linear chains and ring polymers which lack chain ends.