Nanofluidic transport is ubiquitous in natural systems, from extracellular communication in biology to geological phenomena, and promotes the emergence of new technologies such as energy harvesting and water desalination. While experimental access to ultraconfined fluids has advanced rapidly, their behavior challenges conventional theoretical descriptions based on Poisson-Boltzmann theory or the Stokes equation, whose possible extension remains an open question. In this study, we use molecular dynamics simulations to investigate ionic transport within wetting films of water confined on silica surfaces down to the sub-nanometer scale. We then analyze these results using a simple one-dimensional theoretical framework. Remarkably, we show that this model remains valid even at confinement close to the molecular scale. Our results reveal that ion dynamics play a key role in ionic transport through ion adsorption at the water-silica interface. Adsorbed cations do not participate in ionic conduction but instead generate molecular-scale roughness and transmit additional frictional forces to the substrate. This mechanism produces an apparent viscosity increase in electrostatically driven flows, reaching up to four times the bulk value in the case of potassium. Our findings highlight the critical role of interfacial ion adsorption in nanoscale hydrodynamics and provide new insights for interpreting experiments and designing nanofluidic systems.

Most organic and inorganic surfaces (e.g., glass or lipid membranes) become charged in aqueous solutions. The resulting ionic distribution induces effective interactions between the charged surfaces, which depend on the permittivity of the confined aqueous solution. To explore this phenomenon in very confined systems, we perform all-atom molecular dynamics (MD) simulations of charged lipid membranes separated by a salted water layer of varying thickness. To extract an effective permittivity from the atomistic model, we compare the ion distributions of these simulations with the ones of a continuous, mesoscopic model: a modified Poisson–Boltzmann (mPB) equation taking into account a spatially varying dielectric permittivity and an explicit Born solvation energy for ions. Such mPB/MD comparisons, applied to lipid membranes at various hydration levels, reveal a sharp decrease of the permittivity upon dehydration, converging to a plateau value that we attribute to lipid headgroups. We discuss the limitations of the mPB model in the dehydrated lipid membranes, in particular through the appearance of ion/ion correlations, and compare our results to alternative computational methods. In our tension-free simulations of the fluid membranes, an increase in the area per lipid indicates that the permittivity decrease is accompanied by intermembrane attraction. Our approach could be generalized to estimate a mesoscopic permittivity of liquids confined by other interfaces, provided ions follow Boltzmann statistics.

This study investigates the interplay between Strong Coupling (SC) attraction and hydration repulsion in nanoconfined water between like-charged phospholipid layers. We combine reflectivities with numerical simulations to analyze supported phospholipid layers under different relative humidity and surface charge densities. X-ray fluorescence demonstrates that we can control the valence of the associated counterions. Experimental measurement of the water thickness, combined with the precise determination of charged surface positions by numerical simulations, clearly demonstrates the existence of electrostatic attraction in the presence of monovalent counterions. It enables us to compare our experiments with a theoretical model showing that charge-screening by hydration water induces SC attraction, even at moderate surface charge densities with monovalent counterions. Furthermore, hydration repulsion is stronger for DPPS compared with DPPC. These findings offer insights into the forces that control interactions between phospholipid layers and have important implications for biological and colloidal systems.

The Poisson-Boltzmann (PB) equation provides a mean-field theory of electrolyte solutions at interfaces and in confinement, describing how ions reorganize close to charged surfaces to form the so-called electrical double layer (EDL), with numerous applications ranging from colloid science to biology. This formulary focuses on situations of interest for micro- and nanofluidics, and gathers important formulas for the PB description of a Z:Z electrolyte solution inside slit and cylindrical channels. Different approximated solutions (thin EDLs, no co-ion, Debye-Huckel, and homogeneous/parabolic potential limits) and their range of validity are discussed, together with the full solution for the slit channel. Common boundary conditions are presented, the thermodynamics of the EDL is introduced, and an overview of the application of the PB framework to the description of electrokinetic effects is given. Finally, the limits of the PB framework are briefly discussed, and Python scripts to solve the PB equation numerically are provided.

In this study, we carried out equilibrium molecular dynamics (EMD) simulations of the liquid-liquid (LL) interface between two different Lennard-Jones components with varying miscibility, where we examined the relation between the interfacial tension and the free energy to completely isolate the two liquids using both a mechanical and thermodynamic approach. Using the mechanical approach, we obtained a stress distribution around a quasi-one-dimensional EMD system with a flat LL interface. From the stress distribution, we calculated the LL interfacial tension based on Bakker's equation, which uses the stress anisotropy around the interface, and measured how it varied with miscibility. The second approach uses thermodynamic integration by enforcing quasi-static isolation of the two liquids to calculate the free energy. This uses the same EMD systems as the mechanical approach, with both extended dry-surface and phantom-wall (PW) schemes applied. When the two components were immiscible, the mechanical interfacial tension and isolation free energy were in good agreement. When the components were miscible, the values were significantly different. From the result of PW for the case of completely mixed liquids, the difference was attributed to the additional free energy required to separate the binary mixture into single components against the osmotic pressure prior to the complete detachment of the two components. This provides a new route to obtain the free energy of mixing.

Thermo-osmotic flows, generated by applying a thermal gradient along a liquid-solid interface, could be harnessed to convert waste heat into electricity. While this phenomenon has been known for almost a century, there is a crucial need to gain a better understanding of the molecular origins of thermo-osmosis. In this paper, we start by detailing the multiple contributions to thermo-osmosis. We then showcase three approaches to computing the thermo-osmotic coefficient using molecular dynamics; a first method based on the computation of the interfacial enthalpy excess and Derjaguin's theoretical framework, a second approach based on the computation of the interfacial entropy excess using the so-called dry-surface method, and a novel non-equilibrium method to compute the thermo-osmotic coefficient in a periodic channel. We show that the three methods align with each other, in particular for smooth surfaces. In addition, for a polarised graphene-water interface, we observe large variations of thermo-osmotic responses, and multiple changes in flow direction with increasing surface charge. Overall, this study showcases the versatility of osmotic flows and calls for experimental investigation of thermo-osmotic behaviour in the vicinity of charged surfaces.

Thermo-osmotic flows, generated at liquid-solid interfaces by thermal gradients, can be used to produce electric currents from waste heat on charged surfaces. The two key parameters controlling the thermo-osmotic current are the surface charge and the interfacial enthalpy excess due to liquid-solid interactions. While it has been shown that the contribution from water to the enthalpy excess can be crucial, how this contribution is affected by surface charge remained to be understood. Here, we start by discussing how thermo-osmotic flows and induced electric currents are related to the interfacial enthalpy excess. We then use molecular dynamics simulations to investigate the impact of surface charge on the interfacial enthalpy excess, for different distributions of the surface charge, and two different wetting conditions. We observe that surface charge has a strong impact on enthalpy excess, and that the dependence of enthalpy excess on surface charge depends largely on its spatial distribution. In contrast, wetting has a very small impact on the charge-enthalpy coupling. We rationalize the results with simple analytical models, and explore their consequences for thermo-osmotic phenomena. Overall, this work provides guidelines to search for systems providing optimal waste heat recovery performance.

Heat transfer through the interface between a metallic nanoparticle and an electrolyte solution, has great importance in a number of applications, ranging from nanoparticle-based cancer treatments to nanofluids and solar energy conversion devices. However, the impact of surface charge and the dissolved ions on heat transfer has been scarcely explored so far. In this study, we compute the interface thermal conductance between hydrophilic and hydrophobic charged gold nanoparticles immersed in an electrolyte using equilibrium molecular dynamics simulations. Compared with an uncharged nanoparticle, we report a threefold increase of the Kapitza conductance for a nanoparticle surface charge +2 e/nm2. This enhancement is shown to be approximately independent of surface wettability, charge spatial distribution, and salt concentration. This allows us to express the Kapitza conductance enhancement in terms of surface charge density on a master curve. Finally, we interpret the increase of the Kapitza conductance as a combined result of a shift in the water density distribution toward the charged nanoparticle and an accumulation of the counter-ions around the nanoparticle surface which increase the Coulombic interaction between the liquid and the charged nanoparticle.

When a contact line (CL)-where a liquid-vapor interface meets a substrate-is put into motion, it is well known that the contact angle differs between advancing and receding CLs. Using non-equilibrium molecular dynamics simulations, we reveal another intriguing distinction between advancing and receding CLs: while temperature increases at an advancing CL-as expected from viscous dissipation, we show that temperature can drop at a receding CL. Detailed quantitative analysis based on the macroscopic energy balance around the dynamic CL showed that the internal energy change of the fluid due to the change of the potential field along the pathline out of the solid-liquid interface induced a remarkable temperature drop around the receding CL, in a manner similar to latent heat upon phase changes. This result provides new insights for modeling the dynamic CL, and the framework for heat transport analysis introduced here can be applied to a wide range of nanofluidic systems.

The effect of temperature on friction and slip at the liquid-solid interface has attracted attention over the last 20 years, both numerically and experimentally. However, the role of temperature on slip close to the glass transition has been less explored. Here we use molecular dynamics to simulate a bidisperse atomic fluid, which can remain liquid below its melting point (supercooled state), to study the effect of temperature on friction and slip length between the liquid and a smooth apolar wall in a broad range of temperatures. At high temperatures, an Arrhenius law fits well the temperature dependence of viscosity, friction, and slip length. In contrast, when the fluid is supercooled, the viscosity becomes super-Arrhenian, while interfacial friction can remain Arrhenian or even drastically decrease when lowering the temperature, resulting in a massive increase of the slip length. We rationalize the observed superlubricity by the surface crystallization of the fluid, and the incommensurability between the structures of the fluid interfacial layer and of the wall. This study calls for experimental investigation of the slip length of supercooled liquids on low surface energy solids.

Liquid and ionic transport through nanometric structures is central to many phenomena, ranging from cellular exchanges to water resource management or green energy conversion. While pushing down toward molecular scales progressively unveils novel transport behaviors, reaching ultimate confinement in controlled systems remains challenging and has often involved 2D Van der Waals materials. Here, we propose an alternative route which circumvents demanding nanofabrication steps, partially releases material constraints, and offers continuously tunable molecular confinement. This soft-matter-inspired approach is based on the spontaneous formation of a molecularly thin liquid film onto fully wettable substrates in contact with the vapor phase of the liquid. Using silicon dioxide substrates, water films ranging from angstrom to nanometric thicknesses are formed in this manner, and ionic transport within the film can then be measured. Performing conductance measurements as a function of confinement in these ultimate regimes reveals a one-molecule thick layer of fully hindered transport nearby the silica, above which continuum, bulk-like approaches account for experimental results. Overall, this work paves the way for future investigations of molecular scale nanofluidics and provides insights into ionic transport nearby high surface energy materials such as natural rocks and clays, building concretes, or nanoscale silica membranes used for separation and filtering.

Heat transfer through the interface between a metallic nanoparticle and an electrolyte solution has great importance in a number of applications, ranging from nanoparticle-based cancer treatments to nanofluids and solar energy conversion devices. However, the impact of the surface charge and dissolved ions on heat transfer has been scarcely explored so far. In this study, we compute the interface thermal conductance between hydrophilic and hydrophobic charged gold nanoparticles immersed in an electrolyte using equilibrium molecular dynamics simulations. Compared with an uncharged nanoparticle, we report a 3-fold increase of the Kapitza conductance for a nanoparticle surface charge of +320 mC/m2. This enhancement is shown to be approximately independent of the surface wettability, charge spatial distribution, and salt concentration. This allows us to express the Kapitza conductance enhancement in terms of the surface charge density on a master curve. Finally, we interpret the increase of the Kapitza conductance as a combined result of the shift of the water density distribution toward the charged nanoparticle and an accumulation of the counterions around the nanoparticle surface which increase the Coulombic interaction between the liquid and the charged nanoparticle. These considerations help us to apprehend the role of ions in heat transfer close to electrified surfaces.

Lubricated friction is controlled by the contact operating conditions, including temperature, normal load and sliding. In the elastohydrodynamic (EHD) regime, the rheological characteristics of the lubricants are also dependent on these conditions. Under extreme contact conditions (high load, high sliding), a possible friction plateau (limiting shear stress phenomena) can appear, making friction independent of the sliding speed. Since the physical origin of this friction plateau remains unclear, despite many efforts from the tribology community, predicting friction in EHD contact is still challenging. This work introduces an original EHD friction prediction approach built on a completely independent process from the tribological test. It consists of implementing two models a viscosity model based on the rheological experiment and molecular dynamics simulation data combined with a thermal-elastohydrodynamic contact model. Two fluids with different natures are studied squalane and benzyl benzoate. Friction predictions, including friction plateau and thermal effects, are obtained for both fluids and compared with experimental friction measurements, and a quantitative agreement is obtained. In addition, the role of the thermal effects on EHD friction and the origin of the friction plateau are investigated.

Solid-liquid friction plays a key role in nanofluidic systems. Following the pioneering work of Bocquet and Barrat, who proposed to extract the friction coefficient (FC) from the plateau of the Green-Kubo (GK) integral of the solid-liquid shear force autocorrelation, the so-called plateau problem has been identified when applying the method to finite-sized molecular dynamics simulations, e.g., with a liquid confined between parallel solid walls. A variety of approaches have been developed to overcome this problem. Here, we propose another method that is easy to implement, makes no assumptions about the time dependence of the friction kernel, does not require the hydrodynamic system width as an input, and is applicable to a wide range of interfaces. In this method, the FC is evaluated by fitting the GK integral for the timescale range where it slowly decays with time. The fitting function was derived based on an analytical solution of the hydrodynamics equations [Oga et al., Phys. Rev. Res. 3, L032019 (2021)], assuming that the timescales related to the friction kernel and the bulk viscous dissipation can be separated. By comparing the results with those of other GK-based methods and non-equilibrium molecular dynamics, we show that the FC is extracted with excellent accuracy by the present method, even in wettability regimes where other GK-based methods suffer from the plateau problem. Finally, the method is also applicable to grooved solid walls, where the GK integral displays complex behavior at short times.

Among all fluids, water has always been of special concern for scientists from a broad variety of research fields due to its rich behavior. In particular, some questions remain unanswered nowadays concerning the temperature dependence of bulk and interfacial transport properties of supercooled and liquid water, e.g. regarding the fundamentals of the violation of the Stokes-Einstein relation in the supercooled regime or the subtle relation between structure and dynamical properties. Here we investigated the temperature dependence of the bulk transport properties from ab initio molecular dynamics based on density functional theory, down to the supercooled regime. We determined from a selection of functionals, that SCAN better describes the experimental viscosity and self-diffusion coefficient, although we found disagreements at the lowest temperatures. For a limited set of temperatures, we also explored the role of nuclear quantum effects on water dynamics using ab initio molecular dynamics that has been accelerated via a recently introduced machine learning approach. We then investigated the molecular mechanisms underlying the different functionals performance and assessed the validity of the Stokes-Einstein relation. We also explored the connection between structural properties and the transport coefficients, verifying the validity of the excess entropy scaling relations for all the functionals. These results pave the way to predict the transport coefficients from the radial distribution function, helping to develop better functionals. On this line, they indicate the importance of describing the long-range features of the radial distribution function.

Our Society is in high need of alternatives to fossil fuels. Nanoporous systems filled with aqueous electrolytes show great promises for harvesting the osmotic energy of sea water or waste heat. At the core of energy conversion in such nanofluidic systems lie the so-called electrokinetic effects, coupling thermodynamic gradients and fluxes of different types (hydrodynamical, electrical, chemical, thermal) at electrified water-solid interfaces. This chapter starts by introducing the framework of linear irreversible thermodynamics, and how the latter can be used to describe the direct and coupled responses of a fluidic system, providing general relations between the different response coefficients. The chapter then focuses on the so-called osmotic flows, generated by non-hydrodynamic actuation at liquid-solid interfaces, and illustrate how the induced fluxes can be related to the microscopic properties of the water-solid interface. Finally, the chapter moves to electricity production from non-electric actuation, and discusses in particular the performance of nanofluidic systems for the harvesting of osmotic energy and waste heat.

Thermo-osmotic flows - flows generated in micro and nanofluidic systems by thermal gradients - could provide an alternative approach to harvest waste heat. However, such use would require massive thermo-osmotic flows, which are up to now only predicted for special and expensive materials. Thus, there is an urgent need to design affordable nanofluidic systems displaying large thermo-osmotic coefficients. In this paper, we propose a general model for thermo-osmosis of aqueous electrolytes in charged nanofluidic channels, taking into account hydrodynamic slip, together with the different solvent and solute contributions to the thermo-osmotic response. We apply this model to a wide range of systems by studying the effects of wetting, salt type and concentration, and surface charge. We show that intense thermo-osmotic flows can be generated using slipping charged surfaces. We also predict for intermediate wettings a transition from a thermophobic to a thermophilic behavior depending on the surface charge and salt concentration. Overall, this theoretical framework opens an avenue for controlling and manipulating thermally induced flows with common charged surfaces and a pinch of salt.

Unlike crystalline solids or ideal gases, transport properties remain difficult to describe from a microscopic point of view in liquids, whose dynamics result from complex energetic and entropic contributions at the atomic scale. Two scenarios are generally proposed: one represents the dynamics in a fluid as a series of energy-barrier crossings, leading to Arrhenius-like laws, while the other assumes that atoms rearrange themselves by collisions, as exemplified by the free volume model. To assess the validity of these two views, we computed, using molecular dynamics simulations, the transport properties of the Lennard-Jones fluid and tested to what extent the Arrhenius equation and the free volume model describe the temperature dependence of the viscosity and of the diffusion coefficient at fixed pressure. Although both models reproduce the simulation results over a wide range of pressure and temperature covering the liquid and supercritical states of the Lennard-Jones fluid, we found that the parameters of the free volume model can be estimated directly from local structural parameters, also obtained in the simulations. This consistency of the results gives more credibility to the free volume description of transport properties in liquids.

The search for materials with high thermal resistance has promising applications in thermoelectric devices and boiling crisis retardation. In this paper, we study the interfacial heat transfer between water and gold, nanostructuring the gold surface and coating it with graphene. By trapping air (or vacuum in our simulations) between graphene and the nanopatterned surface, we observe a considerable increase in the interfacial resistance compared to the planar gold situation, which is shown to scale with the effective graphene-gold contact surface for both monolayer and multilayer graphene. With the massive thermal resistances we predict (up to 200 nm in terms of Kapitza length), the system proposed here represents a robust alternative to superhydrophobic Cassie materials. Moreover, since the low thermal conductance is achieved primarily due to geometry (vacuum trapping), it is straightforward to extend our results to any material with a structure equivalent to that of the nanopatterned gold wall considered here. Published under an exclusive license by AIP Publishing.