An optimized united atom model for simulations of polymethylene melts

Abstract

We present here an optimized united atom model that is able to reproduce properties of melts of n-alkane chains of varying molecular weights. This model differs from previous models in that the Lennard-Jones well depth for the terminal methyl group (0.2264 kcal/mol) differs from that of the methylene units (0.093 kcal/mol). The position of the minimum is at 4.5 Å for both units. Properties of n-C44H90 melts from this model are compared with experiments and those from an explicit atom model. Good agreement with experiment is obtained for static properties of the melt, specifically P-V-T behavior, chain conformations, and x-ray scattering profiles. The large-scale dynamics, as measured by self-diffusion, are found to agree reasonably well with experimental results, being about 30% faster with our best united atom force field. Analysis of the end-to-end vector orientation autocorrelation function in terms of the Rouse model yields a monomer friction coefficient somewhat greater than that determined from the rate of self-diffusion, reflecting the fact that the n-C44H90 chains are not sufficiently long to behave as Gaussian coils. Detailed local chain dynamics for n-C44H 90 melts, as measured by the P1(t) and P2(t) orientation autocorrelation functions for C-H vectors, are found to agree reasonably well with results from simulations using an explicit atom model, and yield spin-lattice relaxation times T1 and nuclear Overhauser enhancement values in reasonable agreement with experimental 13C NMR measurements. As with large scale dynamics, local dynamics are faster in general (about 20%) than experimental results. © 1995 American Institute of Physics.