Where the linearized Poisson-Boltzmann cell model fails: the planar case as a prototype study.
The linearized Poisson-Boltzmann (PB) approximation is investigated for the classical problem of two infinite, uniformly charged planes in electrochemical equilibrium with an infinite monovalent salt reservoir. At the nonlinear level, we obtain an explicit expression of the associated electrostatic contribution to the semi-grand-canonical potential. The linearized osmotic-pressure difference between the interplane region and the salt reservoir becomes negative in the low-temperature, large-separation, or high-surface charge limits, in disagreement with the exact (at mean-field level) nonlinear PB solution. We show that these artifacts--although thermodynamically consistent with quadratic expansions of the nonlinear functional--can be traced back to the nonfulfillment of the underlying assumptions of the linearization. Explicit comparison between the analytical expressions of the exact nonlinear solution and the corresponding linearized equations allows us to show that the linearized results are asymptotically exact in the weak-coupling and counterionic ideal-gas limits, but always fail otherwise, predicting negative osmotic-pressure differences. By taking appropriate limits of the full nonlinear PB solution, we provide asymptotic expressions for the semi-grand-canonical potential and the osmotic-pressure difference that involve only elementary functions, which cover the complementary region where the linearized theory breaks down.
Tamashiro
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Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany.
Schiessel
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