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The modified Poisson-Boltzmann theory of the restricted primitive modeldouble layer is revisited and recast in a fresh, slightly broader perspective.Derivation of relevant equations follow the techniques utilized in the earlierMPB4 and MPB5 formulations and clarifies the relationship between these. TheMPB4, MPB5, and a new formulation of the theory are employed in an analysis ofthe structure and charge reversal phenomenon in asymmetric 2:1/1:2 valenceelectrolytes. Furthermore, polarization induced surface charge amplification isstudied in 3:1/1:3 systems. The results are compared to the corresponding MonteCarlo simulations. The theories are seen to predict the "exact" simulation datato varying degrees of accuracy ranging from qualitative to almost quantitative.The results from a new version of the theory are found to be of comparableaccuracy as the MPB5 results in many situations. However, in some casesinvolving low electrolyte concentrations, theoretical artifacts in the form ofun-physical "shoulders" in the singlet ionic distribution functions areobserved.

condensed matter physics

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