Conformation of a polymer chain in solution: An exact density expansion approach

摘要

The conformation of a polymer chain in solution is intrinsically coupled to the thermodynamic and structural properties of the solvent. Here we study such solvent effects in a system consisting of a flexible interaction-site n-mer chain immersed in a monomeric solvent. Chain conformation is described with a set of intramolecular site-site probability functions. We derive an exact density expansion for these intramolecular probability functions and give a diagrammatic representation of the terms contributing at each order of the expansion. The expansion is tested for a short hard-sphere chain (n=3 or 4) with site diameter sigma in a hard-sphere solvent with solvent diameter D. In comparison with Monte Carlo simulation results for 0.2less than or equal toD/sigmaless than or equal to100, the expansion (taken to second order) is found to be quantitatively accurate for low to moderate solvent volume fractions for all size ratios. Average chain dimensions are predicted accurately up to liquidlike solvent densities. The hard-sphere chains are compressed with both increasing solvent density and decreasing solvent size. For small solvent (D