We develop a polymer field-theoretic
model that incorporates
explicit
treatment of semiflexibility and polar solvents, providing a framework
to determine the impact of solvent ordering and concentration fluctuations
on the thermodynamic behavior of polyelectrolyte solutions. We study
the effect of dipole ordering on the electrostatic potential near
a charged surface and the phase behavior of oppositely charged symmetric
polyelectrolytes. The phase diagrams, incorporating quadratic-order
concentration fluctuation corrections, are determined using different
approximations of the chain structure factor for semiflexible polymers.
While wormlike-chain statistics provides the most broadly accurate
prediction for phase behavior, a Gaussian-rigid interpolation remains
an adequate approximation for quadratic-order fluctuation corrections
for many experimentally relevant systems. However, our theory provides
the basis for predicting the impact of higher-order concentration
fluctuations, which requires chain statistics that cannot be rendered
from existing approximate methods.
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