Although aqueous electrolytes are among the most important solutions, the molecular simulation of their intertwined properties of chemical potentials, solubility and activity coefficients has remained a challenging problem, and has attracted considerable recent interest. In this perspectives review, we focus on the simplest case of aqueous sodium chloride at ambient conditions and discuss the two main factors that have impeded progress. The first is lack of consensus with respect to the appropriate methodology for force field (FF) development. We examine how most commonly used FFs have been developed, and emphasize the importance of distinguishing between "Training Set Properties" used to fit the FF parameters, and "Test Set Properties", which are pure predictions of additional properties. The second is disagreement among solubility results obtained, even using identical FFs and thermodynamic conditions. Solubility calculations have been approached using both thermodynamic--based methods and direct molecular dynamics--based methods implementing coexisting solution and solid phases. Although convergence has been very recently achieved among results based on the former approach, there is as yet no general agreement with simulation results based on the latter methodology. We also propose a new method to directly calculate the electrolyte standard chemical potential in the Henry-Law ideality model. We conclude by making recommendations for calculating solubility, chemical potentials and activity coefficients, and outline a potential path for future progress.
Lithium chloride LiCl is widely used as a prototype system to study the strongly dissociated 1-1 electrolyte solution. Here, we combined experimental measurements and classical molecular dynamics simulations to study the ion conduction in this system. Ionic conductivities were reported at both 20$^\circ$C and 50$^\circ$C from experiments and compared to results from molecular dynamics simulations. The main finding of this work is that transference numbers of Li$^+$ and Cl$^-$ become comparable at high concentration. This phenomenon is independent of the force fields employed in the simulation …
The study of the modification of interfacial properties between an organic solvent and aqueous electrolyte solutions is presented by using electrostatic Dissipative Particle Dynamics (DPD) simulations. In this article the parametrization for the DPD repulsive parameters aij for the electrolyte components is calculated considering the dependence of the Flory-Huggins \c{hi} parameter on the concentration and the kind of electrolyte added, by means of the activity coefficients. In turn, experimental data was used to obtain the activity coefficients of the electrolytes as a function of their conce…
Nuclear magnetic resonance relaxometry represents a powerful tool for extracting dynamic information. Yet, obtaining links to molecular motion is challenging for many ions that relax through the quadrupolar mechanism, which is mediated by electric field gradient fluctuations and lacks a detailed microscopic description. For sodium ions in aqueous electrolytes, we combine ab initio calculations to account for electron cloud effects with classical molecular dynamics to sample long-time fluctuations, and obtain relaxation rates in good agreement with experiments over broad concentration and tempe…
Ion distribution in aqueous electrolytes near the interface plays critical roles in electrochemical, biological and colloidal systems and is expected to be particularly significant inside nanoconfined regions. Electroneutrality of the total charge inside nanoconfined regions is commonly assumed a priori in solving ion distribution of aqueous electrolytes nanoconfined by uncharged hydrophobic surfaces with no direct experimental validation. Here, we use a quantitative nuclear magnetic resonance approach to investigate the properties of aqueous electrolytes nanoconfined in graphitic-like nanopor…
The Seeebeck coefficients of the non-aqueous electrolytes tetrabutylammonium nitrate, tetraoctylphosphonium bromide and tetradodecylammonium nitrate in 1-octanol, 1-dodecanol and ethylene-glycol are measured in a temperature range from T=30 to T=45 C. The Seebeck coefficient is generally of the order of a few hundreds of microvolts per Kelvin for aqueous solution of inorganic ions. Here we report huge values of 7 mV/K at 0.1M concentration for tetrabutylammonium nitrate in 1-dodecanol. These striking results open the question of unexpectedly large kosmotrope or "structure making" effects of te…
We study, using Density Functional theory and Monte Carlo simulations, aqueous electrolyte solutions between charged infinite planar surfaces, in a contact with a bulk salt reservoir. In agreement with recent experimental observations [Z. Luo et al., Nat. Comm. 6, 6358 (2015)], we find that the confined electrolyte lacks local charge neutrality. We show that a Density Functional Theory (DFT) based on a bulk- HNC expansion properly accounts for strong electrostatic correlations and allows us to accurately calculate the ionic density profiles between the charged surfaces, even for electrolytes c…
The increase of aqueous solubility of nonpolar compounds upon cooling and the cold denaturation of proteins are established experimental facts. Both phenomena have been hypothesized to be related to restructuring of the hydrogen bond network of water around small nonpolar solutes or hydrophobic amino acid side chains. However, an underlying physical mechanism has yet to be identified. We assume the solute particles and the monomers of a polymer interact via a hard sphere potential. We further assume that the solvent molecules interact via the two-scale spherically symmetric Jagla potential, wh…
In spite of a large number of papers published in the last twenty years in the literature, the basic model of liquid water is still controversial. We have measured the dielectric permittivity of pure water and aqueous chlorides solutions in the range 0.2 to 1.5 THz and we have found that the overall dielectric behavior can be satisfactorily described with the weighted average of two single time constant Debye functions. The weights of the two components have been obtained by infrared spectra analysis and are related to two populations of water molecules having a different long range organizati…
Conventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these properties can often be elucidated via the coordination environment of the cation. We develop a theory for the coordination shell of cations in non-aqueous solvent mixtures that can be applied with high fidelity, up to super-concentrated electrolytes. Our theory can naturally explain simulation and experimental values of cation solvation in ''classical'' non-aqueous e…
Transport properties of concentrated electrolytes have been analyzed using classical molecular dynamics simulations with the algorithms and parameters typical of simulations describing complex electrokinetic phenomena. The electrical conductivity and transport numbers of electrolytes containing monovalent (KCl), divalent (MgCl$_2$), a mixture of both (KCl + MgCl$_2$), and trivalent (LaCl$_3$) cations have been obtained from simulations of the electrolytes in electric fields of different magnitude. The results obtained for different simulation parameters have been discussed and compared with ex…
Mean spherical approximation (MSA), second-order Barker-Henderson (BH) perturbation theory and thermodynamic perturbation theory (TPT) for associating fluids in combination with BH perturbation theory are applied to the study of the structural properties and phase behaviour of the Derjaguin-Landau-Verwey-Overbeek (DLVO) model of lysozyme and $γ$-cristalline aqueous electrolyte solutions. Predictions of the MSA for the structure factors are in good agreement with the corresponding computer simulation predictions. The agreement between theoretical results for the liquid-gas phase diagram and the…
Using molecular dynamics simulations, we reveal emergent properties of hydrated electrode interfaces that while molecular in origin are integral to the behavior of the system across long times scales and large length scales. Specifically, we describe the impact of a disordered and slowly evolving adsorbed layer of water on the molecular structure and dynamics of the electrolyte solution adjacent to it. Generically, we find that densities and mobilities of both water and dissolved ions are spatially heterogeneous in the plane parallel to the electrode over nanosecond timescales. These and other…
We theoretically study the size effect of water molecule clusters not only on electrostatic interaction between two charged surfaces in an aqueous electrolyte but also on electroosmotic transport in a nanofluidic channel. Applying a free energy based mean-field approach accounting for different sizes of ions and water molecule clusters, we derive a set of coupled equations to compute electrostatic and electroosmotic properties between charged surfaces. We verify that the smaller the size of a water cluster, the stronger the electroosmotic transport in nanofluidic channels. In addition, we find…
The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-Hückel models to calculate activity coefficients of aqueous mixtures of most important salts in chemistry. The explosion of parameters originates from the phenomenological extension of the Debye-Hückel theory that does not take steric and correlation effects of ions and water into account. In contrast, the Poisson-Fermi theory developed in recent years treats ions and water molecules as nonuniform hard spheres of any size with interstitial voids and includes ion-water and…
Recent experiments and a series of subsequent theoretical studies suggest the occurrence of universal underscreening in highly concentrated electrolyte solutions. We performed a set of systematic Atomic Force Spectroscopy measurements for aqueous salt solutions in a concentration range from 1 mM to 5 M using chloride salts of various alkali metals as well as mixed concentrated salt solutions (involving both mono- and divalent cations and anions), that mimic concentrated brines typically encountered in geological formations. Experiments were carried out using flat substrates and submicrometer-s…
Molecular dynamics simulations of aqueous electrolytes generally rely on empirical force fields, combining dispersion interactions - described by a truncated Lennard-Jones (LJ) potential - and electrostatic interactions - described by a Coulomb potential computed with a long-range solver. Recently, force fields using rescaled ionic charges (electronic continuum correction, ECC), possibly complemented with rescaling of LJ parameters (electronic continuum correction rescaled, ECCR), have shown promising results in bulk, but their performance at interfaces has been less explored. Here we started …
Na-montmorillonite is a natural clay mineral and is available in abundance in nature. The aqueous dispersions of charged and anisotropic platelets of this mineral exhibit non-ergodic kinetically arrested states ranging from soft glassy phases dominated by interparticle repulsions to colloidal gels stabilized by salt induced attractive interactions. When the salt concentration in the dispersing medium is varied systematically, viscoelasticity and yield stress of the dispersion show non-monotonic behavior at a critical salt concentration, thus signifying a morphological change in the dispersion …
Two of the most challenging tasks in molecular simulation consist in capturing the properties of systems with long-range interactions (e.g. electrolyte solutions) as well as systems containing large molecules such as hydrogels. For the development and optimization of molecular force fields and models, a large number of simulation runs have to be evaluated to obtain the sensitivity of the target properties with respect to the model parameters. The present work discusses force field development for electrolytes regarding thermodynamic properties of their aqueous solutions. Furthermore, simulatio…
Nanoporosity in silicon results in an interface-dominated mechanics, fluidics and photonics that are often superior to the ones of the bulk material. However, their active control, e.g. as a response to electronic stimuli, is challenging due to the absence of intrinsic piezoelectricity in the base material. Here, for large-scale nanoporous silicon cantilevers wetted by aqueous electrolytes, we show electrosorption-induced mechanical stress generation of up to 600 kPa that is reversible and adjustable at will by electrical potential variations of approximately 1 V. Laser cantilever bending expe…
Understanding dielectric spectra can reveal important information about the dynamics of solvents and solutes from the dipolar relaxation times down to electronic ones. In the late 1970s, Hubbard and Onsager predicted that adding salt ions to a polar solution would result in a reduced dielectric permittivity that arises from the unexpected tendency of solvent dipoles to align opposite to the applied field. So far, this effect has escaped an experimental verification, mainly because of the concomitant appearance of dielectric saturation from which the Hubbard-Onsager decrement cannot be easily s…
Electrokinetic flows of an aqueous NaCl solution in nanochannels with negatively charged surfaces are studied using molecular dynamics (MD) simulations. The four transport coefficients that characterise the response to weak electric and pressure fields, namely the coefficients for the electrical current in response to the electric field ($M^{jj}$) and the pressure field ($M^{jm}$), and those for the mass flow in response to the same fields ($M^{mj}$ and $M^{mm}$), are obtained in the linear regime using a Green--Kubo approach. Nonequilibrium simulations with explicit external fields are also c…
Macroscopic strain experiments revealed that Si crystals traversed by parallel, channel-like nanopores functionalized with the muscle polymer polypyrrole exhibit large and reversible electrochemo-mechanical actuation in aqueous electrolytes. On the microscopical level this system still bears open questions, as to how the electrochemical expansion and contraction of PPy acts on to np-Si pore walls and how the collective motorics of the pore array emerges from the single-nanopore behavior. An analysis of in operando X-ray diffraction experiments with micromechanical finite element simulations, b…
Properties of aqueous electrolyte solutions at carbon electrodes: effects of concentration and surface charge on solution structure, ion clustering and thermodynamics in the electric double layer
Theoretical calculations of the conductivity of sodium nitrate in water are presented and compared with experimental measurements. The method of direct correlation force in the framework of the interionic theory is used for the calculation of transport properties in connection with the associative mean spherical approximation (AMSA). The effective interactions between ions in solutions are derived with the help of Monte Carlo and Molecular Dynamics calculations on the Born-Oppenheimer level. This work is based on earlier theoretical and experimental studies of the structure of concentrated aqu…
A recent version of statistical associating fluid theory (SAFT), namely SAFT2, is coupled with the van der Waals and Platteeuw theory to study the alkane hydrate phase equilibrium conditions. The model is found to provide an accurate representation of the alkane hydrate dissociation conditions with and without inhibitors, such as salts, alcohols, as well as mixed salts and alcohol. Based on SAFT2, a heterosegmented SAFT equation of state is developed to model the thermodynamic properties of aqueous ionic liquid (IL) solutions, which is recently discovered as dual function gas hydrate inhibitor…
Long-range ion induced water-water correlations were recently observed in femtosecond elastic second harmonic scattering experiments of electrolyte solutions. To further the qualitative understanding of these correlations, we derive an analytical expression that quantifies ion induced dipole-dipole correlations in a non-interacting gas of dipoles. This model is a logical extension of Debye-Hückel theory that can be used to qualitatively understand how the combined electric field of the ions induces correlations in the orientational distributions of the water molecules in an aqueous solution. T…
We study the electro-hydrodynamics of the Debye screening layer that arises in an aqueous binary solution near a planar insulating wall when applying a spatially modulated AC-voltage. Combining this with first order perturbation theory we establish the governing equations for the full non-equilibrium problem and obtain analytic solutions in the bulk for the pressure and velocity fields of the electrolyte and for the electric potential. We find good agreement between the numerics of the full problem and the analytics of the linear theory. Our work provides the theoretical foundations of circuit…
Aqueous electrolyte solutions under the influence of a temperature gradient can generate thermoelectric fields, which arise from different responses of the positive and negative charges. This is related to the thermo diffusion effect which is quantified by the ionic heat of transport and the thermal diffusion coefficient. When a solution is confined between two metallic electrodes with different temperatures, it is expected to measure the electrostatic potential difference due to the thermoelectric field. We performed experiments in aqueous electrolyte solutions, and our results show that a th…
We establish experimentally the flow patterns of induced-charge electro-osmosis (ICEO) around immobilized metallic spheres in aqueous electrolyte. The AC field modifies local electrolyte concentration and causes quadrupolar flows with inward velocities being smaller than the outward ones. At high fields, the flow becomes irregular, with vortices smaller than the size of the sphere. Janus metallo-dielectric spheres create dipolar flows and pump the fluid from the dielectric toward the metallic part. The experimentally determined far-field flows decay with the distance as r-3.
Electrolyte theories enable to describe the structural and dynamical properties of simple electrolytes in solution, such as sodium chloride in water. Using these theories for aqueous solutions of charged nanoparticles is a straightforward route to extract their charge and size from experimental data. Nevertheless, for such strongly asymmetric electrolytes, the validity of the underlying approximations have never been properly challenged with exact simulation results. In the present work, well established mesoscopic numerical simulations are used to challenge the ability of advanced electrolyte…
In this communication we illustrate the occurrence of a recently reported new phenomenon of surface-charge amplification, SCA, (originally dubbed overcharging, OC), [Jimenez-Angeles F. and Lozada-Cassou M., J. Phys. Chem. B, 2004, 108, 7286] by means of molecular dynamics simulation of aqueous electrolytes solutions involving multivalent cations in contact with charged graphene walls and the presence of short-chain lithium polystyrene sulfonates where the solvent water is described explicitly with a realistic molecular model. We show that the occurrence of SCA in these systems, in contrast to …
Massively-parallel molecular dynamics simulation is applied to systems containing electrolytes, vapour-liquid interfaces, and biomolecules in contact with water-oil interfaces. Novel molecular models of alkali halide salts are presented and employed for the simulation of electrolytes in aqueous solution. The enzymatically catalysed hydroxylation of oleic acid is investigated by molecular dynamics simulation taking the internal degrees of freedom of the macromolecules into account. Thereby, Ewald summation methods are used to compute the long range electrostatic interactions. In systems with a …
