Statistical field theory of ion–molecular solutions

Abstract

<p>Schematic representation of the multipolar molecule surrounded by salt ions in a dielectric solvent medium.</p>

Electrochemistry meets polymer physics: polymerized ionic liquids on an electrified electrode

“…The length k −1 can be considered as a measure of the "periodicity" of positive and negative charge-rich domains, which is the result of the fine interplay between the conformation entropy of the polymer chains, electrostatic interactions, and excluded volume interactions of monomeric units. We would like to mention that similar behavior of the electrostatic potential of the point-like charge has been recently predicted in salt solutions of quadrupolar molecules [55][56][57] and ionic liquids with an account of the quadrupolar ionic clusters 48 .…”

Electric double layer theory for room temperature ionic liquids on charged electrodes: milestones and prospects

“…As it has been lately shown, the occurrence of the nonlocal terms in the electrostatic free energy can be explained by the presence of quadrupolar ionic clusters in the RTIL bulk [37]. In this case, the correlation length has the meaning of quadrupolar length [46,47,48,49]. Note that the dipolar clusters (ionic pairs), as it was shown in papers [36,37], make a contribution to the RTIL dielectric constant.…”

“…4, agree with each other, despite the incorrect boundary condition. The problem of the boundary conditions in the mean-field-like theories stems from the fact that the microscopic EDL theory must be essentially nonlocal, while the account of the gradient contributions to the electrostatic free energy density is associated with the truncation of the power series in the wave vector of the dielectric function, ε(k), at the quadratic term [37,44,49]. We note that the authors of papers [50,51] made an attempt to overcome the ambiguity of the boundary condition choice for electrolyte solutions on electrified surface and in confinement.…”

Theory of ionic liquids with polarizable ions on a charged electrode

“…Accounting for the specific interactions between ions and their specific adsorption onto the electrode allows to arrive at capacitance values that are comparable to the experimental values 4 . Moreover, we do not explicitly consider the formation of ionic pairs 27 contributing to the dielectric permittivity and quadrupolar ionic clusters resulting in the electrostatic potential oscillations at long distances from the electrode 26 or point-like test charge 36,37 . Finally, we do not take into account the electrostatic correlations leading to the nonlocal terms in the electrostatic free energy functional 38,39 .…”