Consistent description of ion-specificity in bulk and at interfaces by solvent implicit simulations and mean-field theory

Abstract

Solvent-implicit Monte Carlo (MC) simulations and mean-field theory are used to predict activity coefficients and excess interfacial tensions for NaF, NaCl, NaI, KF, KCl, and KI solutions in good agreement with experimental data over the entire experimentally available concentration range. The effective ionic diameters of the solvent-implicit simulation model are obtained by fits to experimental activity coefficient data. The experimental activity coefficients at high salt concentrations are only reproduced if the ion-specific concentration-dependent decrement of the dielectric constant is included. The dielectric-constant dependent contribution of the single-ion solvation free energy to the activity coefficient is significant and is included. To account for the ion-specific excess interfacial tension of salt solutions, in addition to non-ideal solution effects and the salt-concentration-dependent dielectric decrement, an ion-specific ion–interface interaction must be included. This ion–interface interaction, which acts in addition to the dielectric image-charge repulsion, is modeled as a box potential, is considerably more long-ranged than the ion radius, and is repulsive for all ions considered except iodide, in agreement with previous findings and arguments. By comparing different models that include or exclude bulk non-ideal solution behavior, dielectric decrement effects, and ion–interface interaction potentials, we demonstrate how bulk and interfacial ion-specific effects couple and partially compensate each other. Our MC simulations, which correctly include ionic correlations and interfacial dielectric image-charge repulsion, are used to determine effective ion–surface interaction potentials that can be used in a modified Poisson–Boltzmann theory.