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A classical non-polarizable force field for the common halide (F-, Cl-, Br-, and I-) and alkali (Li+, Na+, K+, and Cs+) ions in SPC/E water is presented. This is an extension of the force field developed by Loche et al. for Na+, K+, Cl-, and Br- (JPCB 125, 8581-8587, 2021): in the present work, we additionally optimize Lennard-Jones parameters for Li+, I-, Cs+, and F- ions. Li+ and F- are particularly challenging ions to model due to their small size. The force field is optimized with respect to experimental solvation free energies and activity coefficients, which are the necessary and sufficient quantities to accurately reproduce the electrolyte thermodynamics. Good agreement with experimental reference data is achieved for a wide range of concentrations (up to 4 mol/l). We find that standard Lorentz-Berthelot combination rules are sufficient for all ions except F-, for which modified combination rules are necessary. With the optimized parameters, we show that, although the force field is only optimized based on thermodynamic properties, structural properties are reproduced quantitatively, while ion diffusion coefficients are in qualitative agreement with experimental values., (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC) license (https://creativecommons.org/licenses/by-nc/4.0/).)

From the stability of colloidal suspensions to the charging of electrodes, electric double layers play a pivotal role in aqueous systems. The interactions between interfaces, water molecules, ions and other solutes making up the electrical double layer span length scales from Ångströms to micrometers and are notoriously complex. Therefore, explaining experimental observations in terms of the double layer's molecular structure has been a long-standing challenge in physical chemistry, yet recent advances in simulations techniques and computational power have led to tremendous progress. In particular, the past decades have seen the development of a multiscale theoretical framework based on the combination of quantum density functional theory, force-field based simulations and continuum theory. In this Review, we discuss these theoretical developments and make quantitative comparisons to experimental results from, among other techniques, sum-frequency generation, atomic-force microscopy, and electrokinetics. Starting from the vapor/water interface, we treat a range of qualitatively different types of surfaces, varying from soft to solid, from hydrophilic to hydrophobic, and from charged to uncharged.

The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg 2+ and SO 4 2- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO 4 2- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO 4 2- ions around 1100 cm -1 reveals a specific slow-down of solvation dynamics for hydrated MgSO 4 and for Na 2 SO 4 in the presence of Mg 2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na 2 SO 4 solutions in the absence of Mg 2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO 4 2- -Mg 2+ ion pairs., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Understanding the collective behavior of ions at charged surfaces is of paramount importance for geological and electrochemical processes. Ions screen the surface charge, and interfacial fields break the centro-symmetry near the surface, which can be probed using second-order nonlinear spectroscopies. The effect of electrolyte concentration on the nonlinear optical response has been semi-quantitatively explained by mean-field models based on the Poisson-Boltzmann equation. Yet, to explain previously reported ion-specific effects on the spectroscopic response, drastic ion-specific changes in the interfacial properties, including surface acidities and dielectric permittivities, or strong ion adsorption/desorption had to be invoked. Here, we use sum-frequency generation (SFG) spectroscopy to probe the symmetry-breaking of water molecules at a charged silica surface in contact with alkaline metal chloride solutions (LiCl, NaCl, KCl, and CsCl) at various concentrations. We find that the water response varies with the cation: the SFG response is markedly enhanced for LiCl compared to CsCl. We show that within mean-field models, neither specific ion-surface interactions nor a reduced dielectric constant of water near the interface can account for the variation of spectral intensities with cation nature. Molecular dynamics simulations confirm that the decay of the electrochemical potential only weakly depends on the salt type. Instead, the effect of different salts on the optical response is indirect, through the reorganization of the interfacial water: the salt-type-dependent alignment of water directly at the interface can explain the observations.

Using classical molecular dynamics simulations, we investigate the dielectric properties at interfaces of water with graphene, graphite, hexane, and water vapor. For graphite, we compare metallic and nonmetallic versions. At the vapor-liquid water and hexane-water interfaces, the laterally averaged dielectric profiles are significantly broadened due to interfacial roughness and only slightly anisotropic. In contrast, at the rigid graphene surface, the dielectric profiles are strongly anisotropic and the perpendicular dielectric profile exhibits pronounced oscillations and sign changes. The interfacial dielectric excess, characterized by the shift of the dielectric dividing surface with respect to the Gibbs dividing surface, is positive for all surfaces, showing that water has an enhanced dielectric response at hydrophobic surfaces. The dielectric dividing surface positions vary significantly among the different surfaces, which points to pronounced surface-specific dielectric behavior. The interfacial repulsion of a chloride ion is shown to be dominated by electrostatic interactions for the soft fluid-fluid interfaces and by non-electrostatic Lennard-Jones interactions for the rigid graphene-water interface. A linear tensorial dielectric model for the ion-interface interaction with sharp dielectric interfaces located on the dielectric dividing surface positions works well for graphene but fails for vapor and hexane, because these interfaces are smeared out. The repulsion of chloride from the metallic and nonmetallic graphite versions differs very little, which reflects the almost identical interfacial water structure and can be understood based on linear continuum dielectric theory. Interface flexibility shows up mostly in the nonlinear Coulomb part of the ion-interface interaction, which changes significantly close to the interfaces and signals the breakdown of linear dielectric continuum theory.

Although important for atmospheric processes and gas-phase catalysis, very little is known about the hydration state of ions in the vapor phase. Here we study the evaporation energetics and kinetics of a chloride ion from liquid water by molecular dynamics simulations. As chloride permeates the interface, a water finger forms and breaks at a chloride separation of ≈ 2.8 nm from the Gibbs dividing surface. For larger separations from the interface, about 7 water molecules are estimated to stay bound to chloride in saturated water vapor, as corroborated by continuum dielectrics and statistical mechanics models. This ion hydration significantly reduces the free-energy barrier for evaporation. The effective chloride diffusivity in the transition state is found to be about 6 times higher than in bulk, which reflects the highly mobile hydration dynamics as the water finger breaks. Both effects significantly increase the chloride evaporation flux from the quiescent interface of an electrolyte solution, which is predicted from reaction kinetic theory., (© 2022. The Author(s).)