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

We present theoretical arguments and numerical results to 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) approximately s/rho R3(s) approximately c(e)/sqrt[s] when connecting two segments together where s denotes the curvilinear length of a segment, R(s) its typical size, c(e) approximately 1/rho b(e)3 the "swelling coefficient," b(e) 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 b(e) and the swelling coefficient c(e) 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 briefly considered.