Ard Louis

Abstract:

Many-body interactions and correlations in coarse-grained descriptions of polymer solutions were studied using Monte Carlo simulations. The effective density dependent two-body potentials that exactly reproduced the pair-correlations between the center of mass (c.m.) of the self avoiding walk polymers were also studied. The results showed that a pair potential cannot simultaneously reproduce the two- and three-body correlations in a system with many-body interactions.

Abstract:

We calculate the two-, three-, four-, and five-body (state-independent) effective potentials between the centers of mass (c.m.'s) of self-avoiding walk polymers by Monte Carlo simulations. For full overlap, these coarse-grained n-body interactions oscillate in sign as (-1)(n), and decrease in absolute magnitude with increasing n. We find semiquantitative agreement with a scaling theory, and use this to discuss how the coarse-grained free energy converges when expanded to arbitrary order in the many-body potentials. We also derive effective density dependent two-body potentials that exactly reproduce the pair-correlations between the c.m. of the self avoiding walk polymers. The density dependence of these pair potentials can be largely understood from the effects of the density independent three-body potential. Triplet correlations between the c.m. of the polymers are surprisingly well, but not exactly, described by our coarse-grained effective pair potential picture. In fact, we demonstrate that a pair potential cannot simultaneously reproduce the two- and three-body correlations in a system with many-body interactions. However, the deviations that do occur in our system are very small, and can be explained by the direct influence of three-body potentials.