The intermolecular structure of semidilute polymer solutions is studied theoretically. The low-density limit of a generalized Ornstein–Zernicke integral equation approach to polymeric liquids is considered. Scaling laws for the dilute-to-semidilute crossover of the random-phase approximation (RPA)-like structure are derived for the intermolecular structure factor on large distances when intermolecular excluded volume is incorporated at the microscopic level. This leads to a nonlinear equation for the excluded volume interaction parameter. For macromolecular size-mass scaling exponents ν above a spatial-dimension dependent value, ${\nu }_c=2/d,$ mean-field-like density scaling is recovered, but for $\nu <{\nu }_c$ the density scaling becomes nontrivial in agreement with field-theoretic results and justifying phenomenological extensions of the RPA. The structure of the polymer mesh in semidilute solutions is discussed in detail and comparisons with large-scale Monte Carlo simulations are added. Finally, a possibility to determine the correction to scaling exponent ${\omega }_{12}$ is suggested.

• Received 12 February 1999

DOI:https://doi.org/10.1103/PhysRevE.60.1921