On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends

The self-consistent field (SCF) theory of dense polymer liquids assumes that short-range correlations are almost independent of how monomers are connected into polymers. Some limits of this idea are explored in the context of a perturbation theory for mixtures of structurally identical polymer species, A and B, in which the AB pair interaction differs slightly from the AA and BB interaction, and the difference is controlled by a parameter alpha Expanding the free energy to O(\alpha) yields an excess free energy of the form alpha $z(N)\phi_{A}\phi_{B}$, in both lattice and continuum models, where z(N) is a measure of the number of inter-molecular near neighbors of each monomer in a one-component liquid. This quantity decreases slightly with increasing N because the self-concentration of monomers from the same chain is slightly higher for longer chains, creating a deeper correlation hole for longer chains. We analyze the resulting $N$-dependence, and predict that $z(N) = z^{\infty}[1 + \beta \bar{N}^{-1/2}]$, where $\bar{N}$ is an invariant degree of polymerization, and $\beta=(6/\pi)^{3/2}$. This and other predictions are confirmed by comparison to simulations. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of coefficients in this perturbation theory to the limit $N \to \infty$. We show that a renormalized one-loop theory contains a quantitatively correct description of the $N$-dependence of local structure studied here.Comment: submitted to J. Chem. Phy

Universality of subleading corrections for self-avoiding walks in presence of one dimensional defects

We study three-dimensional self-avoiding walks in presence of a one-dimensional excluded region. We show the appearance of a universal sub-leading exponent which is independent of the particular shape and symmetries of the excluded region. A classical argument provides the estimate: $\Delta = 2 \nu - 1 \approx 0.175(1)$. The numerical simulation gives $\Delta = 0.18(2)$.Comment: 29 pages, latex2

An improved perturbation approach to the 2D Edwards polymer -- corrections to scaling

We present the results of a new perturbation calculation in polymer statistics which starts from a ground state that already correctly predicts the long chain length behaviour of the mean square end--to--end distance $\langle R_N^2 \rangle\$, namely the solution to the 2~dimensional~(2D) Edwards model. The $\langle R_N^2 \rangle$ thus calculated is shown to be convergent in $N$, the number of steps in the chain, in contrast to previous methods which start from the free random walk solution. This allows us to calculate a new value for the leading correction--to--scaling exponent~$\Delta$. Writing $\langle R_N^2 \rangle = AN^{2\nu}(1+BN^{-\Delta} + CN^{-1}+...)$, where $\nu = 3/4$ in 2D, our result shows that $\Delta = 1/2$. This value is also supported by an analysis of 2D self--avoiding walks on the {\em continuum}.Comment: 17 Pages of Revtex. No figures. Submitted to J. Phys.