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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).)

We developed a global X-ray data analysis method to determine the intrinsic curvatures of lipids hosted in inverted hexagonal phases. In particular, we combined compositional modelling with molecular shape-based arguments to account for non-linear mixing effects of guest-in-host lipids on intrinsic curvature. The technique was verified by all-atom molecular dynamics simulations and applied to sphingomyelin and a series of phosphatidylcholines and ceramides with differing composition of the hydrocarbon chains. We report positive lipid curvatures for sphingomyelin and all phosphatidylcholines with disaturated and monounsaturated hydrocarbons. Phosphatidylcholines with diunsaturated hydrocarbons in turn yielded intrinsic lipid curvatures with negative values. All ceramides, with chain lengths varying between C2:0 and C24:0, displayed significant negative lipid curvature values. Moreover, we report non-additive mixing for C2:0 ceramide and sphingomyelin. This suggests for sphingolipids that in addition to lipid headgroup and hydrocarbon chain volumes also lipid-specific interactions are important contributors to membrane curvature stress., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Modification of surface properties by polymer adsorption is a widely used technique to tune interactions in molecular experiments such as nanopore sensing. Here, we investigate how the ionic current noise through solid-state nanopores reflects the adsorption of short, neutral polymers to the pore surface. The power spectral density of the noise shows a characteristic change upon adsorption of polymer, the magnitude of which is strongly dependent on both polymer length and salt concentration. In particular, for short polymers at low salt concentrations no change is observed, despite the verification of comparable adsorption in these systems using quartz crystal microbalance measurements. We propose that the characteristic noise is generated by the movement of polymers on and off the surface and perform simulations to assess the feasibility of this model. Excellent agreement with experimental data is obtained using physically motivated simulation parameters, providing deep insight into the shape of the adsorption potential and underlying processes. This paves the way toward using noise spectral analysis for in situ characterization of functionalized nanopores.

The poor performance of many existing nonpolarizable ion force fields is typically blamed on either the lack of explicit polarizability, the absence of charge transfer, or the use of unreduced Coulomb interactions. However, this analysis disregards the large and mostly unexplored parameter range offered by the Lennard-Jones potential. We use a global optimization procedure to develop water-model-transferable force fields for the ions K + , Na + , Cl - , and Br - in the complete parameter space of all Lennard-Jones interactions using standard mixing rules. No extra-thermodynamic assumption is necessary for the simultaneous optimization of the four ion pairs. After an optimization with respect to the experimental solvation free energy and activity, the force fields reproduce the concentration-dependent density, ionic conductivity, and dielectric constant with high accuracy. The force field is fully transferable between simple point charge/extended and transferable intermolecular potential water models. Our results show that a thermodynamically consistent force field for these ions needs only Lennard-Jones and standard Coulomb interactions.

The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field., (© 2021. Springer Nature Limited.)

The dielectric constant and the viscosity of water at the interface of hydrophilic surfaces differ from their bulk values, and it has been proposed that the deviation is caused by the strong electric field and the high ion concentration in the interfacial layer. We calculate the dependence of the dielectric constant and the viscosity of bulk electrolytes on the electric field and the salt concentration. Incorporating the concentration and field-dependent dielectric constant and viscosity in the extended Poisson-Boltzmann and Stokes equations, we calculate the electro-osmotic mobility. We compare the results to literature experimental data and explicit molecular dynamics simulations of OH-terminated surfaces and show that it is necessary to additionally include the presence of a subnanometer wide interfacial water layer, the properties of which are drastically transformed by the sheer presence of the interface. We conclude that the origin of the anomalous behavior of aqueous interfacial layers cannot be found in electrostriction or electroviscous effects caused by the interfacial electric field and ion concentration. Instead, it is primarily caused by the intrinsic ordering and orientation of the interfacial water layer.

Ionic surfactants are known to build up higher interfacial pressures at oil/water interfaces than at air/water interfaces for the same surfactant bulk concentration. Here, we systematically investigate this effect through atomistic molecular dynamics (MD) simulations of surfactant-loaded air/water and oil/water interfaces. Two prototypical ionic surfactants, C 12 TAB and sodium dodecyl sulfate (SDS), are studied and found to give consistent results, which are also robust with respect to variations in the simulation force field. The simulations reproduce the experimental interfacial pressure data on a semiquantitative level and reveal that the influence of oil on the surfactants' in-plane distribution is a major contribution to the observed effect, albeit insufficient to be the sole reason. The simulations are further analyzed with regard to surfactant/oil cooperative/competitive effects that have been invoked recently as an explanation. However, the interfacial orientation of oil molecules, a presumable indicator for such behavior, is found to display changes only for high levels of surfactant coverage.

Absorption spectra of liquid water at 300 K are calculated from both classical and density functional theory molecular dynamics simulation data, which together span from 1 MHz to hundreds of THz, agreeing well with experimental data qualitatively and quantitatively over the entire range, including the IR modes, the microwave peak, and the intermediate THz bands. The spectra are decomposed into single-molecular and collective components, as well as into components due to molecular reorientations and changes in induced molecular dipole moments. These decompositions shed light on the motions underlying the librational and translational (hydrogen-bond stretching) bands at 20 and 5 THz, respectively; interactions between donor protons and acceptor lone pair electrons are shown to be important for the line shape in both librational and translational regimes, and in- and out-of-phase librational dimer modes are observed and explored.

Energy dissipation in water is very fast and more efficient than in many other liquids. This behavior is commonly attributed to the intermolecular interactions associated with hydrogen bonding. Here, we investigate the dynamic energy flow in the hydrogen bond network of liquid water by a pump-probe experiment. We resonantly excite intermolecular degrees of freedom with ultrashort single-cycle terahertz pulses and monitor its Raman response. By using ultrathin sample cell windows, a background-free bipolar signal whose tail relaxes monoexponentially is obtained. The relaxation is attributed to the molecular translational motions, using complementary experiments, force field, and ab initio molecular dynamics simulations. They reveal an initial coupling of the terahertz electric field to the molecular rotational degrees of freedom whose energy is rapidly transferred, within the excitation pulse duration, to the restricted translational motion of neighboring molecules. This rapid energy transfer may be rationalized by the strong anharmonicity of the intermolecular interactions., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY).)

The electrification of hydrophobic surfaces is an intensely debated subject in physical chemistry. We theoretically study the ζ potential of hydrophobic surfaces for varying pH and salt concentration by solving the Poisson-Boltzmann and Stokes equations with individual ionic adsorption affinities. Using the ionic surface affinities extracted from the experimentally measured surface tension of the air-electrolyte interface, we first show that the interfacial adsorption and repulsion of small inorganic ions such as H 3 O + , OH - , HCO 3 - , and CO 3 2- cannot account for the ζ potential observed in experiments because the surface affinities of these ions are too small. Even if we take hydrodynamic slip into account, the characteristic dependence of the ζ potential on pH and salt concentration cannot be reproduced. Instead, to explain the sizable experimentally measured ζ potential of hydrophobic surfaces, we assume minute amounts of impurities in the water and include the impurities' acidic and basic reactions with water. We find good agreement between our predictions and the reported experimental ζ potential data of various hydrophobic surfaces if we account for impurities that consist of a mixture of weak acids (p K a = 5-7) and weak bases (p K b = 12) at a concentration of the order of 10 -7 M.

Despite the widespread use of aqueous electrolytes as conductors, the molecular mechanism of ionic conductivity at moderate to high electrolyte concentrations remains largely unresolved. Using a combination of dielectric spectroscopy and molecular dynamics simulations, we show that the absorption of electrolytes at ~0.3 THz sensitively reports on the local environment of ions. The magnitude of these high-frequency ionic motions scales linearly with conductivity for a wide range of ions and concentrations. This scaling is rationalized within a harmonic oscillator model based on the potential of mean force extracted from simulations. Our results thus suggest that long-ranged ionic transport is intimately related to the local energy landscape and to the friction for short-ranged ion dynamics: a high macroscopic electrolyte conductivity is thereby shown to be related to large-amplitude motions at a molecular scale.

The structure of water molecules in contact with zwitterionic lipid molecules is of great biological relevance, because biological membranes are largely composed of such lipids. The interaction of the interfacial water molecules with the amphiphilic lipid molecules drives the formation of membranes and greatly influences various processes at the membrane surface, as the field that arises from the aligned interfacial water molecules masks the charges of the lipid headgroups from the approaching metabolites. To increase our understanding of the influence of water molecules on biological processes we study their structure at the interface using sum-frequency generation spectroscopy and molecular dynamics simulations. Interestingly, we find that water molecules at zwitterionic lipid molecules are mainly oriented by the field arising between the two oppositely charged molecular moieties within the lipid headgroups.

Nonlinear field dependence of electrophoresis in high fields has been investigated theoretically, yet experimental studies have failed to reach consensus on the effect. In this Letter, we present a systematic study on the nonlinear electrophoresis of highly charged submicron particles in applied electric fields of up to several kV/cm. First, the particles are characterized in the low-field regime at different salt concentrations and the surface charge density is estimated. Subsequently, we use microfluidic channels and video tracking to systematically characterize the nonlinear response over a range of field strengths. Using velocity measurements on the single particle level, we prove that nonlinear effects are present at electric fields and surface charge densities that are accessible in practical conditions. Finally, we show that nonlinear behavior leads to unexpected particle trapping in channels.

Many vital processes taking place in electrolytes, such as nanoparticle self-assembly, water purification, and the operation of aqueous supercapacitors, rely on the precise many-body interactions between surfaces and ions in water. Here we study the interaction between a hydrated ion and a charge-neutral graphene layer using atomistic molecular dynamics simulations. For small separations, the ion-graphene repulsion is of nonelectrostatic nature, and for intermediate separations, van der Waals attraction becomes important. Contrary to prevailing theory, we show that nonlinear and tensorial dielectric effects become non-negligible close to surfaces, even for monovalent ions. This breakdown of standard isotropic linear dielectric theory has important consequences for the understanding and modeling of charged objects at surfaces.

We study the ion density, shear viscosity and electroosmotic mobility of an aqueous monovalent electrolyte at a charged solid surface using molecular dynamics simulations. Upon increasing the surface charge density, ions are displaced first from the diffuse layer to the outer Helmholtz layer, increasing its viscosity, and subsequently to the hydrodynamically stagnant inner Helmholtz layer. The ion redistribution causes both charge inversion and reversal of the electroosmotic mobility. Because of the surface-charge dependent interfacial hydrodynamic properties, however, the charge density of mobility reversal differs from the charge density of charge inversion, depending on the salt concentration and the chemical details of the ions and the surface. Mobility reversal cannot be described by an effective slip boundary condition alone - the spatial dependence of the viscosity is essential.

We construct an analytical model to account for the influence of the subnanometer-wide interfacial layer on the differential capacitance and the electro-osmotic mobility of solid-electrolyte interfaces. The interfacial layer is incorporated into the Poisson-Boltzmann and Stokes equations using a box model for the dielectric properties, the viscosity, and the ionic potential of mean force. We calculate the differential capacitance and the electro-osmotic mobility as a function of the surface charge density and the salt concentration, both with and without steric interactions between the ions. We compare the results from our theoretical model with experimental data on a variety of systems (graphite and metallic silver for capacitance and titanium oxide and silver iodide for electro-osmotic data). The differential capacitance of silver as a function of salinity and surface charge density is well reproduced by our theory, using either the width of the interfacial layer or the ionic potential of mean force as the only fitting parameter. The differential capacitance of graphite, however, needs an additional carbon capacitance to explain the experimental data. Our theory yields a power-law dependence of the electro-osmotic mobility on the surface charge density for high surface charges, reproducing the experimental data using both the interfacial parameters extracted from molecular dynamics simulations and fitted interfacial parameters. Finally, we examine different types of hydrodynamic boundary conditions for the power-law behavior of the electro-osmotic mobility, showing that a finite-viscosity layer explains the experimental data better than the usual hydrodynamic slip boundary condition. Our analytical model thus allows us to extract the properties of the subnanometer-wide interfacial layer by fitting to macroscopic experimental data.

We compare the dielectric spectra of aqueous MgSO 4 and Na 2 SO 4 solutions calculated from classical molecular dynamics simulations with experimental data, using an optimized thermodynamically consistent sulfate force field. Both the concentration-dependent shift of the static dielectric constant and the spectral shape match the experimental results very well for Na 2 SO 4 solutions. For MgSO 4 solutions, the simulations qualitatively reproduce the experimental observation of a slow mode, the origin of which we trace back to the ion-pair relaxation contribution via spectral decomposition. The radial distribution functions show that Mg 2+ and SO 4 2- ions form extensive water-separated-and thus strongly dipolar-ion pairs, the orientational relaxation of which provides a simple physical explanation for the prominent slow dielectric mode in MgSO 4 solutions. Remarkably, the Mg 2+ -SO 4 2- ion-pair relaxation extends all the way into the THz range, which we rationalize by the vibrational relaxation of tightly bound water-separated ion pairs. Thus, the relaxation of divalent ion pairs can give rise to widely separated orientational and vibrational spectroscopic features.

On the basis of the Poisson-Boltzmann equation in cylindrical coordinates, we calculate the conductivity of a single charged nanotube filled with electrolyte. The conductivity as a function of the salt concentration follows a power-law, the exponent of which has been controversially discussed in the literature. We use the co-ion-exclusion approximation and obtain the crossover between different asymptotic power-law behaviors analytically. Numerically solving the full Poisson-Boltzmann equation, we also calculate the complete diagram of exponents as a function of the salt concentration and the pH for tubes with different radii and p K a values. We apply our theory to recent experimental results on carbon nanotubes using the p K a as a fit parameter. In good agreement with the experimental data, the theory shows power-law behavior with the exponents 1/3 at high pH and 1/2 at low pH, with a crossover depending on salt concentration, tube radius and p K a .

Using a box profile approximation for the non-electrostatic surface adsorption potentials of anions and cations, we calculate the differential capacitance of aqueous electrolyte interfaces from a numerical solution of the Poisson-Boltzmann equation, including steric interactions between the ions and an inhomogeneous dielectric profile. Preferential adsorption of the positive (negative) ion shifts the minimum of the differential capacitance to positive (negative) surface potential values. The trends are similar for the potential of zero charge; however, the potential of zero charge does not correspond to the minimum of the differential capacitance in the case of asymmetric ion adsorption, contrary to the assumption commonly used to determine the potential of zero charge. Our model can be used to obtain more accurate estimates of ion adsorption properties from differential capacitance or electrocapillary measurements. Asymmetric ion adsorption also affects the relative heights of the characteristic maxima in the differential capacitance curves as a function of the surface potential, but even for strong adsorption potentials the effect is small, making it difficult to reliably determine the adsorption properties from the peak heights.

The electrolyte surface tension exhibits a characteristic minimum around a salt concentration of 1 mM for all ion types, known as the Jones-Ray effect. We show that a consistent description of the experimental surface tension of salts, bases, and acids is possible by assuming charged impurities in the water with a surface affinity typical for surfactants. Comparison with experimental data yields an impurity concentration in the nanomolar range, well below the typical experimental detection limit. Our modeling reveals salt-screening enhanced impurity adsorption as the mechanism behind the Jones-Ray effect: for very low salt concentration added salt screens the  electrostatic repulsion between impurities at the surface, which dramatically increases impurity adsorption and thereby reduces the surface tension.

The surface tension of the air-water interface increases upon addition of inorganic salts, implying a negative surface excess of ionic species. Most acids, however, induce a decrease in surface tension, indicating a positive surface excess of hydrated protons. In combination with the apparent negative charge at pure air-water interfaces derived from electrokinetic experiments, this experimental observation has been a source of intense debate since the mid-19th century. Herein, we calculate surface tensions and ionic surface propensities at air-water interfaces from classical, thermodynamically consistent molecular dynamics simulations. The surface tensions of NaOH, HCl, and NaCl solutions show outstanding quantitative agreement with experiment. Of the studied ions, only H 3 O + adsorbs to the air-water interface. The adsorption is explained by the deep potential well caused by the orientation of the H 3 O + dipole in the interfacial electric field, which is confirmed by ab initio simulations., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

X-ray reflectivity (XR) and atomistic molecular dynamics (MD) simulations, carried out to determine the structure of the oil-water interface, provide new insight into the simplest liquid-liquid interface. For several oils (hexane, dodecane, and hexadecane) the XR shows very good agreement with a monotonic interface-normal electron density profile (EDP) broadened only by capillary waves. Similar agreement is also found for an EDP including a sub-Å thick electron depletion layer separating the oil and the water. The XR and MD derived depletions are much smaller than reported for the interface between solid-supported hydrophobic monolayers and water.

We calculate the power spectrum of electric-field-driven ion transport through nanometer-scale membrane pores using both linearized mean-field theory and Langevin dynamics simulations. Remarkably, the linearized mean-field theory predicts a plateau in the power spectral density at low frequency ω, which is confirmed by the simulations at low ion concentration. At high ion concentration, however, the power spectral density follows a power law that is reminiscent of the 1/ω(α) dependence found experimentally at low frequency. On the basis of simulations with and without ion-ion interactions, we attribute the low-frequency power-law dependence to ion-ion correlations. We show that neither a static surface charge density, nor an increased pore length, nor an increased ion valency have a significant effect on the shape of the power spectral density at low frequency.

We optimize force fields for H3O(+) and OH(-) that reproduce the experimental solvation free energies and the activities of H3O(+) Cl(-) and Na(+) OH(-) solutions up to concentrations of 1.5 mol/l. The force fields are optimized with respect to the partial charge on the hydrogen atoms and the Lennard-Jones parameters of the oxygen atoms. Remarkably, the partial charge on the hydrogen atom of the optimized H3O(+) force field is 0.8 ± 0.1|e|--significantly higher than the value typically used for nonpolarizable water models and H3O(+) force fields. In contrast, the optimal partial charge on the hydrogen atom of OH(-) turns out to be zero. Standard combination rules can be used for H3O(+) Cl(-) solutions, while for Na(+) OH(-) solutions, we need to significantly increase the effective anion-cation Lennard-Jones radius. While highlighting the importance of intramolecular electrostatics, our results show that it is possible to generate thermodynamically consistent force fields without using atomic polarizability.

Many properties of the interfacial layer of water at surfaces differ significantly from those of bulk water. The consequences are most significant for the double-layer capacitance and the electrokinetic properties. We model the interfacial hydration layer by a modified dielectric constant and a modified local viscosity over a single interfacial width. Analytic expressions in the low-charge Debye-Hückel approximation are derived and shown to describe experimental surface capacitance and electro-osmotic data in a unified framework., (© 2015 The Author(s).)

For ion channel gating, the appearance of two distinct conformational states and the discrete transitions between them are essential, and therefore of crucial importance to all living organisms. We show that the physical interplay between two structural elements that are commonly present in bacterial mechanosensitive channels--namely, a charged vestibule and a hydrophobic constriction--creates two distinct conformational states, open and closed, as well as the gating between them. We solve the nonequilibrium Stokes-Poisson-Nernst-Planck equations, extended to include a molecular potential of mean force, and show that a first order transition between the closed and open states arises naturally from the diffusio-osmotic stress caused by the ions and the water inside the channel and the elastic restoring force from the membrane.

Standard continuum theory fails to predict several key experimental results of electrostatic and electrokinetic measurements at aqueous electrolyte interfaces. In order to extend the continuum theory to include the effects of molecular solvent structure, we generalize the equations for electrokinetic transport to incorporate a space dependent dielectric profile, viscosity profile, and non-electrostatic interaction potential. All necessary profiles are extracted from atomistic molecular dynamics (MD) simulations. We show that the MD results for the ion-specific distribution of counterions at charged hydrophilic and hydrophobic interfaces are accurately reproduced using the dielectric profile of pure water and a non-electrostatic repulsion in an extended Poisson-Boltzmann equation. The distributions of Na(+) at both surface types and Cl(-) at hydrophilic surfaces can be modeled using linear dielectric response theory, whereas for Cl(-) at hydrophobic surfaces it is necessary to apply nonlinear response theory. The extended Poisson-Boltzmann equation reproduces the experimental values of the double-layer capacitance for many different carbon-based surfaces. In conjunction with a generalized hydrodynamic theory that accounts for a space dependent viscosity, the model captures the experimentally observed saturation of the electrokinetic mobility as a function of the bare surface charge density and the so-called anomalous double-layer conductivity. The two-scale approach employed here-MD simulations and continuum theory-constitutes a successful modeling scheme, providing basic insight into the molecular origins of the static and kinetic properties of charged surfaces, and allowing quantitative modeling at low computational cost.

We calculate the electro-osmotic mobility and surface conductivity at a solid-liquid interface from a modified Poisson-Boltzmann equation, including spatial variations of the dielectric function and the viscosity that where extracted previously from molecular dynamics simulations of aqueous interfaces. The low-dielectric region directly at the interface leads to a substantially reduced surface capacitance. At the same time, ions accumulate into a highly condensed interfacial layer, leading to the well-known saturation of the electro-osmotic mobility at large surface charge density regardless of the hydrodynamic boundary conditions. The experimentally well-established apparent excess surface conductivity follows from our model for all hydrodynamic boundary conditions without additional assumptions. Our theory fits multiple published sets of experimental data on hydrophilic and hydrophobic surfaces with striking accuracy, using the nonelectrostatic ion-surface interaction as the only fitting parameter.

We derive the theoretical framework to calculate the dielectric response tensor and determine its components for water adjacent to hydrophilic and hydrophobic surfaces using molecular dynamics simulations. For the nonpolarizable water model used, linear response theory is found to be applicable up to an external perpendicular field strength of ∼2 V/nm, which is well beyond the experimental dielectric breakdown threshold. The dipole contribution dominates the dielectric response parallel to the interface, whereas for the perpendicular component it is essential to keep the quadrupole and octupole terms. Including the space-dependent dielectric function in a mean-field description of the ion distribution at a single charged interface, we reproduce experimental values of the interfacial capacitance. At the same time, the dielectric function decreases the electrostatic part of the disjoining pressure between two charged surfaces, unlike previously thought. The difference in interfacial polarizability between hydrophilic and hydrophobic surfaces can be quantized in terms of the dielectric dividing surface. Using the dielectric dividing surface and the Gibbs dividing surface positions to estimate the free energy of a single ion close to an interface, ion-specific adsorption effects are found to be more pronounced at hydrophobic surfaces than at hydrophilic surfaces, in agreement with experimental trends.

Using molecular dynamics simulations we demonstrate pumping of water through a carbon nanotube by time-dependent electric fields. The fields are generated by electrodes with oscillating charges in a broad gigahertz frequency range that are attached laterally to the tube. The key ingredient is a phase shift between the electrodes to break the spatiotemporal symmetry. A microscopic theory based on a polarization-dragging mechanism accounts quantitatively for our numerical findings., (© 2012 American Chemical Society)

The framework for deriving tensorial interfacial dielectric profiles from bound charge distributions is established and applied to molecular dynamics simulations of water at hydrophobic and hydrophilic surfaces. In conjunction with a modified Poisson-Boltzmann equation, the trend of experimental double-layer capacitances is well reproduced. We show that the apparent Stern layer can be understood in terms of the dielectric profile of pure water.

We study water flow through carbon nanotubes using continuum theory and molecular dynamics simulations. The large slip length in carbon nanotubes greatly enhances the pumping and electrokinetic energy conversion efficiency. In the absence of mobile charges, however, the electro-osmotic flow vanishes. Uncharged nanotubes filled with pure water can therefore not be used as electric field-driven pumps, contrary to some recently ventured ideas. This is in agreement with results from a generalized hydrodynamic theory that includes the angular momentum of rotating dipolar molecules. The electro-osmotic flow observed in simulations of such carbon nanotubes is caused by an imprudent implementation of the Lennard-Jones cutoff. We also discuss the influence of other simulation parameters on the spurious electro-osmotic flow.

We theoretically consider the possibility of using electric fields in aqueous channels of cylindrical and planar geometry to induce transport in the absence of mobile ionic charges. Using the Navier-Stokes equation, generalized to include the effects of water spinning, dipole orientation and relaxation, we show analytically that pumping of a dipolar liquid through an uncharged hydrophobic channel can be achieved by injecting torque into the liquid, based on the coupling between molecular spinning and fluid vorticity. This is possible using rotating electric fields and suitably chosen interfacial boundary conditions or transiently by suddenly switching on a homogeneous electric field. A static electric field, however, does not induce a steady state flow in channels, irrespective of the geometry. Using molecular dynamics (MD) simulations, we confirm that static fields do not lead to any pumping, in contrast to earlier publications. The pumping observed in MD simulations of carbon nanotubes and oil droplets in a static electric field is tracked down to an imprudent implementation of Lennard-Jones interaction truncation schemes.

We explore mechanisms for flow generation in water-filled nanochannels, employing the coupling between translational and rotational momentum. Using a generalized Navier-Stokes equation that includes dipolar polarization and relaxation, we show that static electric fields do not induce fluid flow in the planar geometry, while rotating electric fields efficiently convert electric into hydraulic power on the nanoscale. We also perform extensive molecular dynamics simulations of water in nanochannels and find that erroneous force truncation can give rise to spurious flow effects for static electric fields.

Using laser fluorescence microscopy, we study the shape and dynamics of individual DNA molecules in slitlike nanochannels confined to a fraction of their bulk radius of gyration. With a confinement size spanning 2 orders of magnitude, we observe a transition from the de Gennes regime to the Odijk regime in the scaling of both the radius of gyration and the relaxation time. The radius of gyration and the relaxation time follow the predicted scaling in the de Gennes regime, while, unexpectedly, the relaxation time shows a sharp decrease in the Odijk regime. The radius of gyration remains constant in the Odijk regime. Additionally, we report the first measurements of the effect of confinement on the shape anisotropy.

Much is written about "hydrophobic forces" that act between solvated molecules and nonpolar interfaces, but it is not always clear what causes these forces and whether they should be labeled as hydrophobic. Hydrophobic effects roughly fall in two classes, those that are influenced by the addition of salt and those that are not. Bubble adsorption and cavitation effects plague experiments and simulations of interacting extended hydrophobic surfaces and lead to a strong, almost irreversible attraction that has little or no dependence on salt type and concentration. In this paper, we are concerned with hydrophobic interactions between single molecules and extended surfaces and try to elucidate the relation to electrostatic and ion-specific effects. For these nanoscopic hydrophobic forces, bubbles and cavitation effects play only a minor role and even if present cause no equilibration problems. In specific, we study the forced desorption of peptides from nonpolar interfaces by means of molecular dynamics simulations and determine the adsorption potential of mean force. The simulation results for peptides compare well with corresponding AFM experiments. An analysis of the various contributions to the total peptide-surface interactions shows that structural effects of water as well as van der Waals interactions between surface and peptide are important. Hofmeister ion effects are studied by separately determining the effective interaction of various ions with hydrophobic surfaces. An extension of the Poisson-Boltzmann equation that includes the ion-specific potential of mean force yields surface potentials, interfacial tensions, and effective interactions between hydrophobic surfaces. There, we also analyze the energetic contributions to the potential of mean force and find that the most important factor determining ion-specific adsorption at hydrophobic surfaces can best be described as surface-modified ion hydration.

We report on the efficiency of electrical power generation in individual rectangular nanochannels by means of streaming currents, the pressure-driven transport of counterions in the electrical double layer. Our experimental study as a function of channel height and salt concentration reveals that the highest efficiency occurs when double layers overlap, which corresponds to nanoscale fluidic channels filled with aqueous solutions of low ionic strength. The highest efficiency of approximately 3% was found for a 75 nm high channel, the smallest channel measured. The data are well described by Poisson-Boltzmann theory with an additional electrical conductance of the Stern layer.

We theoretically evaluate the prospect of using electrokinetic phenomena to convert hydrostatic energy to electrical power. An expression is derived for the energy conversion efficiency of a two-terminal fluidic device in terms of its linear electrokinetic response properties. For a slitlike nanochannel of constant surface charge density, we predict that the maximum energy conversion efficiency occurs at low salt concentrations. An analytic expression for the regime of strong double-layer overlap reveals that the efficiency depends only on the ratio of the channel height to the Gouy-Chapman length, and the product of the viscosity and the counterion mobility. We estimate that an electrokinetic energy conversion device could achieve a maximum efficiency of 12% for simple monovalent ions in aqueous solution.

The current-voltage characteristics of the alpha-Hemolysin protein pore during the passage of single-stranded DNA under varying ionic strength C are studied experimentally. We observe strong blockage of the current, weak superlinear growth of the current as a function of voltage, and a minimum of the current as a function of C. These observations are interpreted as the result of the ion electrostatic self-energy barrier originating from the large difference in the dielectric constants of water and the lipid bilayer. The dependence of DNA capture rate on C also agrees with our model.