The drying of hydrophobic cavities is believed to play an important role in biophysical phenomena such as the folding of globular proteins, the opening and closing of ligand-gated ion channels, and ligand binding to hydrophobic pockets. We use forward flux sampling, a molecular simulation technique, to compute the rate of capillary evaporation of water confined between two hydrophobic surfaces separated by nanoscopic gaps, as a function of gap, surface size and temperature. Over the range of conditions investigated (gaps between 9 and 14 Å and surface areas between 1 and 9 nm^2) the free energy barrier to evaporation scales linearly with the gap between hydrophobic surfaces, suggesting that line tension makes the predominant contribution to the free energy barrier. The exponential dependence of the evaporation rate on the gap between confining surfaces causes a ten order-of-magnitude decrease in the rate when the gap increases from 9 to 14 Å. The computed free energy barriers are of the order of 50kT, and are predominantly enthalpic. Evaporation rates per unit area are found to be two orders of magnitude faster in confinement by the larger (9 nm^2) than by the smaller (1nm^2) surfaces considered here, at otherwise identical conditions. We show that this is a direct consequence of the dependence of hydrophobic hydration on the size of solvated objects. For sufficiently large surfaces, the critical nucleus for the evaporation process is a gap-spanning cylindrical vapor tube.
When placed on rough hydrophobic surfaces, water droplets of diameter larger than a few millimeters can easily form pearls, as they are in the Cassie-Baxter state with air pockets trapped underneath the droplet. Intriguingly, a natural evaporating process can drive such a Fakir drop into a completely wetting (Wenzel) state. Our microscopic observations with simultaneous side and bottom views of evaporating droplets upon transparent hydrophobic microstructures elucidate the water-filling dynamics and the mechanism of this evaporation-triggered transition. For the present material the wetting tr…
Effect of confinement on the liquid-liquid transition of water are studied by simulations in the Gibbs ensemble. Upon cooling along the liquid-vapor coexistence curve, confined water undergoes transition from normal to strongly tetrahedral water via a first order phase transition (as in the bulk) or in a continuous way in dependence on pore hydrophilicity. In all cases, transition temperature is only slightly shifted by the confinement. This agrees with the experimentally observed weak effect of confinement on the temperature of the fragile-to-strong transition of water.
Molecular dynamic simulations were employed to study a water-like model confined between hydrophobic and hydrophilic plates. The phase behavior of this system is obtained for different distances between the plates and particle-plate potentials. For both hydrophobic and hydrophilic walls there are the formation of layers. Crystallization occurs at lower temperature at the contact layer than at the middle layer. In addition, the melting temperature decreases as the plates become more hydrophobic. Similarly, the temperatures of maximum density and extremum diffusivity decrease with hydrophobicity…
We study the size and shape of the final deposit obtained when a drop with colloidal particles has dried on a super-hydrophobic surface made of micro-posts. As expected, most of the particles lie inside a circular area, which radius roughly corresponds to the Laplace pressure threshold for liquid impalement inside the structure (Cassie-Wenzel transition), inducing a coffee-stain deposit due to contact-line pinning. Less expected is the observation of tiny deposits on top of posts in the area external to the main ring, despite the low macroscopic liquid/solid friction. Experiments are carried o…
We have studied the molecular scale hydrophobicity of an apolar solute, argon, confined between hydrophobic planar surfaces with different confinement widths. Specifically, we find that the hydrophobicity exhibits a non-monotonic behavior with confinement width. While hydrophobicity is usually large compared to bulk value, we find a narrow range of confinement width where the hydrophobicity displays similar values as in bulk water. Furthermore, we develop a simple model taking into account the entropic changes in nanoconfined geometry, which enables us to calculate potential of mean force betw…
Evaporation of surfactant laden sessile droplets is omnipresent in nature and industrial applications such as inkjet printing. Soluble surfactants start to form micelles in an aqueous solution for surfactant concentrations exceeding the critical micelle concentration (CMC). Here, the evaporation of aqueous sodium dodecyl sulfate (SDS) sessile droplets on hydrophobic surfaces were experimentally investigated for SDS concentrations ranging from 0.025 to 1 CMC. In contrast to the constant contact angle of an evaporating sessile water droplet, we observed that, at the same surface the contact angl…
We have used computer simulation to study the collapse of a hydrophobic chain in water. We find that the mechanism of collapse is much like that of a first order phase transition. The evaporation of water in the vicinity of the polymer provides the driving force for collapse, and the rate limiting step is the nucleation of a sufficiently large vapor bubble. The study is made possible through the application of transition path sampling and a coarse grained treatment of liquid water. Relevance of our findings to understanding the folding and assembly of proteins is discussed.
The properties of water can have a strong dependence on the confinement. Here, we consider a water monolayer nanoconfined between hydrophobic parallel walls under conditions that prevent its crystallization. We investigate, by simulations of a many-body coarse-grained water model, how the properties of the liquid are affected by the confinement. We show, by studying the response functions and the correlation length and by performing finite-size scaling of the appropriate order parameter, that at low temperature the monolayer undergoes a liquid-liquid phase transition ending in a critical point…
It has been recently shown that nanobubbles exhibit a remarkable and unexpected stability. The lifetime of nanobubbles, formed either within liquids or on hydrophobic surfaces, can exceed by more than 10 orders of magnitude the theoretical expectation, which predicts an almost immediate dissolution due to the very high Laplace internal pressure in such small bubbles. This unexpected property of nanobubbles has made them leading candidates for energy applications, e.g. as high-pressure nanoreactors in fuel cells, and for biological systems, as transport systems for gas delivery to membranes and…
Using molecular dynamics simulations we study the dynamics of a water-like TIP5P model of water in hydrophilic and hydrophobic confinement. We find that in case of extreme nanocofinement such that there is only one molecular layer of water between the confinement surface, the dynamics of water remains Arrhenius with a very high activation energy up to high temperatures. In case of polar (hydrophilic) confinement, The intermediate time scale dynamics of water is drastically modified presumably due to the transient coupling of dipoles with the effective electric field due to the surface charges.…
In the last decades a large effort has been devoted to the study of water confined in hydrophobic geometries at the nanoscale (tubes, slit pores), because of the multiple technological applications of such systems, ranging from drugs delivery to water desalinization devices. To our knowledge, neither numerical/theoretical nor experimental approaches have so far reached a consensual understanding of structural and transport properties of water under these conditions. In this work, we present molecular dynamics simulations of TIP4P/2005 water under different hydrophobic nano-confinements (slit p…
Nanofluids hold promise for a wide range of areas of industry. However, understanding of wetting behavior and deposition formation in course of drying and spreading of nanofluids, particularly containing surfactants, is still poor. In this paper, the evaporation dynamics of quantum dot-based nanofluids and evaporation-driven self-assembly in nanocolloidal suspensions on hexamethyldisilazane-, polystyrene-, and polypropylene-coated hydrophobic surfaces have been studied experimentally. Moreover, for the very first time, we make a step to understanding of wetting dynamics of superspreader surfac…
Liquid water can become metastable with respect to its vapor in hydrophobic confinement. The resulting dewetting transitions are often impeded by large kinetic barriers. According to macroscopic theory, such barriers arise from the free energy required to nucleate a critical vapor tube that spans the region between two hydrophobic surfaces - tubes with smaller radii collapse, whereas larger ones grow to dry the entire confined region. Using extensive molecular simulations of water between two nanoscopic hydrophobic surfaces, in conjunction with advanced sampling techniques, here we show that f…
We present a Monte Carlo (MC) grid-based model for the drying of drops of a nanoparticle suspension upon a heterogeneous surface. The model consists of a generalised lattice-gas in which the interaction parameters in the Hamiltonian can be varied to model different properties of the materials involved. We show how to choose correctly the interactions, to minimise the effects of the underlying grid so that hemispherical droplets form. We also include the effects of surface roughness to examine the effects of contact-line pinning on the dynamics. When there is a `lid' above the system, which pre…
Molecular dynamics simulations are carried out to explore the dynamical crossover phenomenon in strongly confined and mildly supercooled water in graphene oxide nanopores. In contrast to studies where confinement is used to study the properties of bulk water, we are interested in the dynamical transitions for strongly confined water in the absence of any bulk-like water. The influence of the physicochemical nature of the graphene oxide surface on the dynamical transitions is investigated by varying the extent of hydrophobicity on the confining surfaces placed at an inter-surface separation of …
The evaporation of a tiny amount of water on the solid surface with different wettability has been studied by molecular dynamics simulations. We found that, as the surface changed from hydrophobicity to hydrophility, the evaporation speed did not show a monotonically decrease from intuition, but increased first, and then decreased after reached a maximum value. The competition between the number of the water molecules on the water-gas surface from where the water molecules can evaporate and the potential barrier to prevent those water molecules from evaporating results in the unexpected behavi…
We perform systematic molecular dynamics simulations of water confined between two nanoscale plates at T=300 K. We investigate the effect of pressure (-0.15 GPa <= P <= 0.2 GPa) and plate separation (0.4 nm <= d <= 1.6 nm) on the phase behavior of water when the plates are either hydrophobic or hydrophilic. When water is confined between hydrophobic plates, capillary evaporation occurs between the plates at low enough P. The threshold value of d at which this transition occurs decreases with P (e.g., 1.6 nm at P ~ -0.05 GPa; 0.5 nm at P \~ 0.1 GPa), until, at high P, no capillary evaporation o…
The present article highlights an approach to generate contrasting patterns from drying droplets in a liquid bridge configuration, different from well-known coffee rings. Reduction of the confinement distance (the gap between the solid surfaces) leads to systematized nano-particle agglomeration yielding to spokes-like patterns similar to those found on scallop shells instead of circumferential edge deposition. Alteration of the confinement length modulates the curvature that entails variations in the evaporation flux across the liquid-vapor interface. Consequently, flow inside different liquid…
We present the results of a computer simulation study of thermodynamical properties of TIP4P water confined in a hydrophobic disordered matrix of soft spheres upon supercooling. The hydrogen bond network of water appears preserved in this hydrophobic confinement. Nonetheless a reduction in the average number of hydrogen bonds due to the geometrical constraints is observed. The liquid branch of the spinodal line is calculated from 350 K down to 210 K. The same thermodynamic scenario of the bulk is found: the spinodal curve is monotonically decreasing. The line of maximum density bends avoiding …
Effects of substrate temperature, substrate wettability and particles concentration are experimentally investigated for evaporation of a sessile water droplet containing colloidal particles. Time-varying droplet shapes and temperature of the liquid-gas interface are measured using high-speed visualization and infrared thermography, respectively. The motion of the particles inside the evaporating droplet is qualitatively visualized by an optical microscope and profile of final particle deposit is measured by an optical profilometer. On a non-heated hydrophilic substrate, a ring-like deposit for…
We use Metropolis Monte Carlo and umbrella sampling to calculate the free energies of interaction of two methane molecules and their charged derivatives in cylindrical water-filled pores. Confinement strongly alters the interactions between the nonpolar solutes, and completely eliminates the solvent separated minimum (SSM) that is seen in bulk water. The free energy profiles show that the methane molecules are either in contact or at separations corresponding to the diameter and the length of the cylindrical pore. Analytic calculations that estimate the entropy of the solutes, which are solvat…
The temperature dependence of the structure of water confined in hydrophilic mesostructured porous silica (MCM-41) and hydrophobic benzene-bridged periodic mesoporous organosilicas (PMO) is studied by Raman vibrational spectroscopy. For capillary filled pores (75% relative humidity, RH), the OH-stretching region is dominated by the contribution from liquid water situated in the core part of the pore. It adopts a bulk-like structure that is modestly disrupted by confinement and surface hydrophobicity. For partially filled pores (33% RH), the structure of the non-freezable adsorbed film radicall…
The free energetics of water density fluctuations in bulk water, at interfaces, and in hydrophobic confinement inform the hydration of hydrophobic solutes as well as their interactions and assembly. The characterization of such free energetics is typically performed using enhanced sampling techniques such as umbrella sampling. In umbrella sampling, order parameter distributions obtained from adjacent biased simulations must overlap in order to estimate free energy differences between biased ensembles. Many biased simulations are typically required to ensure such overlap, which exacts a steep c…
Water and water-mediated interactions determine thermodynamic and kinetics of protein folding, protein aggregation and self-assembly in confined spaces. To obtain insights into the role of water in the context of folding problems, we describe computer simulations of a few related model systems. The dynamics of collapse of eicosane shows that upon expulsion of water the linear hydrocarbon chain adopts an ordered helical hairpin structure with 1.5 turns. The structure of dimer of eicosane molecules has two well ordered helical hairpins that are stacked perpendicular to each other. As a prelude t…
Graphene nanochannels are relevant for their possible applications, as in water purification, and for the challenge of understanding how they change the properties of confined liquids. Here, we use all-atom molecular dynamics simulations to investigate water confined in an open graphene slit-pore as a function of its width $w$, down to sub-nm scale. We find that the water translational and rotational dynamics exhibits an oscillatory dependence on $w$, due to water layering. The oscillations in dynamics correlate with those in hydration pressure, which can be negative (hydrophobic attraction), …
In this paper, the pinning and depinning mechanism of the contact line during droplet evaporation on chemically stripe-patterned surfaces is numerically investigated using a thermal multiphase lattice Boltzmann (LB) model with liquid-vapor phase change. A local force balance in the context of diffuse interfaces is introduced to explain the equilibrium states of droplets on chemically patterned surfaces. It is shown that, when the contact line is pinned on a hydrophobic-hydrophilic boundary, different contact angles can be interpreted as the variation of the length of the contact line occupied …
Pathogens in droplets on fomites and aerosols go through extreme physiochemical conditions, such as confinement and osmotic stress, due to evaporation. Still, these droplets are the predominant transmission routes of many contagious diseases. The biggest challenge for studying the survival mechanisms of pathogens in extreme conditions is closely observing them, especially in aerosols, due to the small droplet sizes, movements, and fast evaporative dynamics. To mimic evaporating aerosols and microdroplets, we employ microfluidic emulsion droplets. The presence of oil forms a microdroplet cluste…
Although common in nature, the self-assembly of small molecules at sold-liquid interfaces is difficult to control in artificial systems. The high mobility of dissolved small molecules limits their residence at the interface, typically restricting the self-assembly to systems under confinement or with mobile tethers between the molecules and the surface. Small hydrogen-bonding molecules can overcome these issues by exploiting group-effect stabilization to achieve non-tethered self-assembly at hydrophobic interfaces. Significantly, the weak molecular interactions with the solid makes it possible…
A simple fluid, described by point-like particles interacting via the Lennard-Jones potential, is considered under confinement in a slit geometry between two walls at distance Lz apart for densities inside the vapor-liquid coexistence curve. Equilibrium then requires the coexistence of a liquid "bridge" between the two walls, and vapor in the remaining pore volume. We study this equilibrium for several choices of the wall-fluid interaction (corresponding to the full range from complete wetting to complete drying, for a macroscopically thick film), and consider also the kinetics of state change…
We study by molecular dynamics simulations the thermodynamics of an anomalous fluid confined in a slit pore with one wall structured and attractive and another unstructured and repulsive. We find that the phase diagram of the homogeneous part of the confined fluid is shifted to higher temperatures, densities and pressures with respect to the bulk, but it can be rescaled on the bulk case. We calculate a moderate increase of mobility of the homogeneous confined fluid that we interpret as a consequence of the layering due to confinement and the collective modes due to long-range correlations. We …
Understanding the stabilities of proteins in nanopores requires a quantitative description of confinement induced interactions between amino acid side chains. We use molecular dynamics simulations to study the nature of interactions between the side chain pairs ALA-PHE, SER-ASN and LYS-GLU in bulk water and in water-filled nanopores. The temperature dependence of the bulk solvent potentials of mean force and the interaction free energies in cylindrical and spherical nanopores is used to identify the corresponding entropic and enthalpic components. The entropically stabilized hydrophobic intera…
The magnitude of the pH of the surface of water continues to be a contentious topic in the physical chemistry of aqueous interfaces. Recent theoretical studies have shown little or no preference for the proton to be at the surface compared to the bulk\cite{baer2014toward}. Using ab-initio molecular dynamics simulations, we revisit the propensity of the excess proton for the air-water interface with a particular focus on the role of instantaneous liquid interfaces. We find a much a stronger propensity of the proton for the surface of water. The enhanced water structuring around the proton resul…
Hydrogen bond patterns, proton ordering, and phase transitions of monolayer ice in two-dimensional hydrophobic confinement are fundamentally different from those found for bulk ice. To investigate the behavior of quasi-2D ice, we perform molecular dynamics simulations of water confined between fixed graphene plates at a distance of 0.65 nm. While experimental results are still limited and theoretical investigations are often based on a single force field model, this work presents a systematic study using different water force fields, i.e. SPCE, TIP3P, TIP4P, TIP4P/ICE, TIP5P. The water occupan…
