Size and/or charge asymmetry effects in coulombic fluids in the presence of external fields: an update

In a recent review, “Size and/or charge asymmetry effects in coulombic fluids in the presence of external fields: From simple electrolytes to molten salts”, Guerrero-García, Biophysical Chemistry 282, 106747 (2022), one of the present authors analyzed some consequences of breaking the symmetry in the valence and/or ionic size of charged fluids, such as aqueous electrolytes, macroion solutions, or molten salts, when ion correlations and ionic excluded volume effects were taken into account. In this review article, we would like to discuss some additional effects of breaking the symmetry in the valence and/or size of charged particles of coulombic fluids (i) next to a rigid cylindrical charged polymer, and (ii) in the electrostatic properties of an electrical double layer planar supercapacitor. These effects were studied in approaches beyond the classical non-linear Poisson-Boltzmann theory of point ions, by using classical integral equations theory, the Modified Poisson-Boltzmann theory, and Monte Carlo simulations in implicit solvent. As a result, the relevance of the asymmetry in the valence and/or size of charged particles, at microscopic level, is illustrated here either in simple electrolytes or in aqueous colloidal suspensions of macroions, when both are under the influence of an external electric field.