Virial coefficients and osmotic pressure in polymer solutions in good-solvent conditions

J Chem Phys. 2006 Sep 7;125(9):094903. doi: 10.1063/1.2338913.

Abstract

We determine the second, third, and fourth virial coefficients appearing in the density expansion of the osmotic pressure Pi of a monodisperse polymer solution in good-solvent conditions. Using the expected large-concentration behavior, we extrapolate the low-density expansion outside the dilute regime, obtaining the osmotic pressure for any concentration in the semidilute region. Comparison with field-theoretical predictions and experimental data shows that the obtained expression is quite accurate. The error is approximately 1%-2% below the overlap concentration and rises at most to 5%-10% in the limit of very large polymer concentrations.