Weak violation of universality for Polyelectrolyte Chains: Variational Theory and Simulations

Abstract

A variational approach is considered to calculate the free energy and the conformational properties of a polyelectrolyte chain in $d$ dimensions. We consider in detail the case of pure Coulombic interactions between the monomers, when screening is not present, in order to compute the end-to-end distance and the asymptotic properties of the chain as a function of the polymer chain length $N$. We find $R \simeq N^ν(\log N)^γ$ where $ν= \frac{3}{λ+2}$ and $λ$ is the exponent which characterize the long-range interaction $U \propto 1/r^λ$. The exponent $γ$ is shown to be non-universal, depending on the strength of the Coulomb interaction. We check our findings, by a direct numerical minimization of the variational energy for chains of increasing size $2^4<N<2^{15}$. The electrostatic blob picture, expected for small enough values of the interaction strength, is quantitatively described by the variational approach. We perform a Monte Carlo simulation for chains of length $2^4<N<2^{10}$. The non universal behavior of the exponent $ γ$ previously derived within the variational method, is also confirmed by the simulation results. Non-universal behavior is found for a polyelectrolyte chain in $d=3$ dimension. Particular attention is devoted to the homopolymer chain problem, when short range contact interactions are present.