Intermolecular structural correlations in model globular and unconcatenated ring polymer liquids

Abstract

We employ the field theoretic polymer integral equation theory to construct a segment-level theory for the thermodynamics and pair structure of dense liquids of interpenetrating ring polymers and a simple globule model. The latter is defined by a fractal mass distribution on all internal length scales with an exponent equal to the spatial dimension (d_F = d_s = 3). In an isochoric ensemble the dimensionless compressibility and pressure is predicted to vary exponentially with macromolecular volume fraction. An intermolecular correlation hole exists down to small length scales. This model appears to be useful for a recently studied experimental soft nanoparticle suspension, and also serves as a reference system for our analysis of ring liquids. Motivated by simulations, a two-fractal exponent ring model is adopted for the intramolecular structure factor. At smaller lengths it describes chain-like macromolecules, while on larger scales it corresponds to a space-filling object in the sense that d_F = d_s = 3. The crossover between these two regimes is of order the entanglement length of the linear chain analog. Based on a constant compressibility ensemble, the effective volume fraction grows at intermediate values of degree of polymerization (N), and crosses over to a very slow logarithmic growth at large N. A weaker intermolecular correlation hole is predicted. The number of nearest neighbor rings increases dramatically at small N, akin to linear chain melts, but then tends to saturate at large N, in accord with simulations. The tools developed may be relevant for other partially interpenetrating soft objects such as core–shell nanogels or microgels.