A finite excluded volume bond-fluctuation model: static properties of dense polymer melts revisited.
The classical bond-fluctuation model (BFM) is an efficient lattice Monte Carlo algorithm for coarse-grained polymer chains where each monomer occupies exclusively a certain number of lattice sites. In this paper we propose a generalization of the BFM where we relax this constraint and allow the overlap of monomers subject to a finite energy penalty epsilon. This is done to vary systematically the dimensionless compressibility g of the solution in order to investigate the influence of density fluctuations in dense polymer melts on various static properties at constant overall monomer density. The compressibility is obtained directly from the low-wave vector limit of the static structure factor. We consider, e.g., the intrachain bond-bond correlation function P(s) of two bonds separated by s monomers along the chain. It is shown that the excluded volume interactions are never fully screened for very long chains. If distances smaller than the thermal blob size are probed (s<<g) the chains are swollen according to the classical Fixman expansion where, e.g., P(s) approximately g(-1)s(-1/2). More importantly, the polymers behave on larger distances (s>>g) like swollen chains of incompressible blobs with P(s) approximately g(0)s(-3/2).
Wittmer
J P
JP
Institut Charles Sadron, 23 rue du Loess, 67037 Strasbourg Cédex, France. jwittmer@ics.u-strasbg.fr
Cavallo
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Kreer
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Baschnagel
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Johner
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