Ultrasoft primitive model of polyionic solutions: Structure, aggregation, and dynamics
Résumé
We introduce an ultrasoft core model of interpenetrating polycations and polyanions, with continuous Gaussian charge distributions, to investigate polyelectrolyte aggregation in dilute and semi-dilute salt-free solutions. The model is studied by a combination of approximate theories (random phase approximation and hypernetted chain theory) and numerical simulations. The calculated pair structure, thermodynamics, phase diagram, and polyion dynamics of the symmetric version of the model (the "ultrasoft restricted primitive model" or UPRM) differ from the corresponding properties of the widely studied "restricted primitive model" (RPM) where ions have hard cores. At sufficiently low temperatures and densities, oppositely charged polyions form weakly interacting, polarizable neutral pairs. The clustering probabilities, dielectric behavior, and electrical conductivity point to a line of sharp conductor-insulator transitions in the density-temperature plane. At very low temperatures, the conductor-insulator transition line terminates near the top of a first order coexistence curve separating a high-density liquid phase from a low-density vapor phase. The simulation data hint at a tricritical behavior, reminiscent of that observed for the two-dimensional Coulomb gas, which contrasts with the Ising criticality of its three-dimensional counterpart, the RPM.
Mots clés
dielectric function
electrical conductivity transitions
Gaussian distribution
ionic conductivity
Ising model
numerical analysis
permittivity
phase diagrams
polymer electrolytes
polymer solutions
RPA calculations
thermodynamics
EFFECTIVE PAIR POTENTIALS
STATISTICAL-MECHANICS
PHASE-DIAGRAM
EXCLUDED-VOLUME
DILUTE-SOLUTION
SIMULATION
SYSTEMS
FLUID
ELECTROLYTES
EQUILIBRIUM
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