Intramolecular long-range correlations in polymer melts: The segmental size distribution and its moments

Abstract

Presenting theoretical arguments and numerical results we demonstrate long-range intrachain correlations in concentrated solutions and melts of long flexible polymers which cause a systematic swelling of short chain segments. They can be traced back to the incompressibility of the melt leading to an effective repulsion $u(s)\approx s/\rho R^3(s)\approx ce/\sqrt{s}$ when connecting two segments together where $s$ denotes the curvilinear length of a segment, $R(s)$ its typical size, $ce\approx 1/\rho b{e}^3$ the ``swelling coefficient", $be$ the effective bond length and $\rho$ the monomer density. The relative deviation of the segmental size distribution from the ideal Gaussian chain behavior is found to be proportional to $u(s)$. The analysis of different moments of this distribution allows for a precise determination of the effective bond length $be$ and the swelling coefficient $ce$ of asymptotically long chains. At striking variance to the short-range decay suggested by Flory's ideality hypothesis the bond-bond correlation function of two bonds separated by $s$ monomers along the chain is found to decay algebraically as $1/s^{3/2}$. Effects of finite chain length are considered briefly.

50 pages, 13 figures, submitted to PRE

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