Charge reversal and surface charge amplification in asymmetric valence restricted primitive model planar electric double layers in the modified Poisson-Boltzmann theory

W2759587246 · 수집 2026-10-04 18:12:34

T12274 Electrostatics and Colloid Interactions

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The modified Poisson-Boltzmann theory of the restricted primitive model double layer is revisited and recast&#13;\nin a fresh, slightly broader perspective. Derivation of relevant equations follow the techniques utilized in the&#13;\nearlier MPB4 and MPB5 formulations and clarifies the relationship between these. The MPB4, MPB5, and a&#13;\nnew formulation of the theory are employed in an analysis of the structure and charge reversal phenomenon&#13;\nin asymmetric 2:1/1:2 valence electrolytes. Furthermore, polarization induced surface charge amplification is&#13;\nstudied in 3:1/1:3 systems. The results are compared to the corresponding Monte Carlo simulations. The theories are seen to predict the “exact” simulation data to varying degrees of accuracy ranging from qualitative to&#13;\nalmost quantitative. The results from a new version of the theory are found to be of comparable accuracy as the&#13;\nMPB5 results in many situations. However, in some cases involving low electrolyte concentrations, theoretical&#13;\nartifacts in the form of un-physical “shoulders” in the singlet ionic distribution functions are observed.

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