Coalescence Initiation in Liquid-Liquid Systems: A Stochastic Model.

Coalescence is a complex phenomenon leading to the merging of deformable particles of fluid. The complexity stems largely from the simultaneous occurrence of phenomena of a different nature (hydrodynamic, electrostatic, physicochemical) acting at different scales. The stochastic effects controlling the formation of the liquid bridge between two droplets of the same liquid, immersed in another nonmiscible liquid, are studied through a series of molecular dynamics simulations. The case of heptane droplets in water, relevant to solvent extraction, a key process of the circular economy, is considered. From this series of simulations, we have confirmed that the probability function of coalescence of two identical droplets in contact follows a Poisson distribution. We moreover propose a criterion for the initiation of coalescence based on nucleation theory. A complete description of the stochastic initiation of coalescence is hence provided, opening many perspectives for the simulation of coalescence in continuous approaches used in fluid mechanics and chemical engineering. The methodology can be generalized to droplets of different size and composition, immersed in gas, or to bubbles, i.e., to other physical problems whose kinetics is influenced by the molecular scale.

Cation Adsorption in TiO2 Nanotubes: Implication for Water Decontamination.

TiO2 nanotubes constitute very promising nanomaterials for water decontamination by the removal of cations. We combined a range of experimental techniques from structural analyses to measurements of the properties of aqueous suspensions of nanotubes, with (i) continuous solvent modeling and (ii) quantum DFT-based simulations to assess the adsorption of Cs+ on TiO2 nanotubes and to predict the separation of metal ions. The methodology is set to be operable under realistic conditions, which, in this case, include the presence of CO2 that needs to be treated as a substantial contaminant, both in experiments and in models. The mesoscopic model, based on the Poisson-Boltzmann equation and surface adsorption equilibrium, predicts that H+ ions are the charge-determining species, while Cs+ ions are in the diffuse layer of the outer surface with a significant contribution only at high concentrations and high pH. The effect of the size of nanotubes in terms of the polydispersity and the distribution of the inner and outer radii is shown to be a third-order effect that is very small when the nanotube layer is not very thick (ranging from 1 to 2 nm). Besides, DFT-based molecular dynamics simulations demonstrate that, for protonation, the one-site and successive association assumption is correct, while, for Cs+ adsorption, the size of the cation is important and the adsorption sites should be carefully defined.

Liquid-Liquid Flow at Nanoscale: Slip and Hydrodynamic Boundary Conditions.

Nonequilibrium molecular dynamics (NEMD) simulations have been performed to describe the flow of a fluid nanolayer confined by another fluid. The results show that the behavior of liquids can still be described by the Navier-Stokes equation at the nanoscale, i.e., when only few molecular layers are involved. NEMD furthermore gives additional knowledge on flow. Indeed, while a very small slip is evidenced for a solid-liquid interface as, e.g., in lubrication, the slip lengths are significantly larger at the liquid-liquid interface, as encountered, e.g., in droplet coalescence. The slip lengths of the two fluids are linked. The increase in hydrodynamic slip for liquid-liquid interfaces is attributed to the enhancement of fluid diffusion, which reduces friction.

Why local and non-local terms are essential for second harmonic generation simulation?

Second Harmonic Generation (SHG) today represents one of the most powerful techniques to selectively probe all types of interfaces. However, the origin of the SHG signal at a molecular level is still debated since the local dipole contribution, which is strongly correlated to the molecular orientation can be counterbalanced by non-local quadrupole contributions. Here, we propose a method to simulate the SHG signal of a model water/air interface from the molecular response of each contribution. This method includes both local and non-local terms, which are represented, respectively, by the dependency of the polarisability and hyperpolarisability upon the chemical environment of the molecule and by the bulk quadrupole response. The importance of both terms for the sound simulation of the SHG signals and their interpretation is assessed. We demonstrate that the sole dipole term is unable to simulate a SHG signal, even if the dependency of the hyperpolarisability on the local environment is considered. The inclusion of the bulk quadrupole contribution, which largely dominates the dipole contribution, is essential to predict the SHG response, although the accuracy of the prediction is increased when the dependency upon the local environment is considered.

Experimentally probing ionic solutions in single-digit nanoconfinement.

Understanding ionic solutions in single-digit nanoconfinement is crucial to explain the behavioral transition of confined solutions. This is particularly the case when the system length scale crosses the classical key length scales describing energetics and equilibrium of ionic solutions next to surfaces. Experimentally probing nanoconfinement would open large perspectives to test modelling or theory predictions. Here, using a new test vehicle that consists in 3 and 5 nm-height silica nanochannels associated with an original characterization technique based on the interface hard X-ray reflectivity analysis, we directly probed the transport of solutions containing cations having increasing kosmotropic properties (XCl2 with X: Ba < Ca < Mg) and obtained their distributions inside the nanochannels. We observed that cation adsorption decreases with the size of the confinement and that small cation adsorption is favored. In addition, nanochannel clogging occurs when ions tend to form ion pairs. These ion pairs may play the role of nano-sized prenucleation clusters leading to phase precipitation. These results evidence the specific ion effect in single-digit nanoconfinement that may result in dramatic changes of solution properties. In this line, our new method opens new perspectives for the characterization of ionic solutions and of interfaces in single-digit nanoconfinement.

Deciphering second harmonic generation signals.

Second harmonic generation (SHG) has emerged as one of the most powerful techniques used to selectively monitor surface dynamics and reactions for all types of interfaces as well as for imaging non-centrosymmetric structures, although the molecular origin of the SHG signal is still poorly understood. Here, we present a breakthrough approach to predict and interpret the SHG signal at the atomic level, which is freed from the hyperpolarisability concept and self-consistently considers the non-locality and the coupling with the environment. The direct ab initio method developed here shows that a bulk quadrupole contribution significantly overwhelms the interface dipole term in the purely interfacial induced second-order polarisation for water/air interfaces. The obtained simulated SHG responses are in unprecedented agreement with the experimental signal. This work not only paves the road for the prediction of SHG response from more complex interfaces of all types, but also suggests new insights in the interpretation of the SHG signal at a molecular level. In particular, it highlights the modest influence of the molecular orientation and the high significance of the bulk quadrupole contribution, which does not depend on the interface, in the total experimental response.

Deformation of a Liquid Near an AFM Tip: Molecular Dynamics Approach.

The interaction between an atomic force microscopy (AFM) probe and a thin film of water deposited over a flat substrate is studied using molecular dynamics (MD). The effects of the film thickness and the probe radius on both the deformation height of the liquid interface and the distance of the jump to contact at which the liquid comes in direct contact with the probe are investigated. The dynamics of the surface deformation and the role of interface fluctuations are studied in detail. The systems considered belong to the thin-film regime described in a semianalytical model previously established by Ledesma-Alonso et al. (Langmuir 2013, 29, 7749-7757). MD simulations predict that for shallow films, both the distance at which the jump to contact occurs and the surface maximal deformation height increase steadily with the layer thickness regardless of the probe radius, which is in agreement with the previously proposed theoretical model. The deformation of the surface was shown to be unstable because of the strong effect of thermal fluctuations. For each of the considered systems, the film thickness was such that interface fluctuations induced the jump to contact. The comparison of the deformation obtained in MD with the profiles predicted by the continuous model points out the complementarity between the two approaches. The results of the molecular approach not only are consistent with those of the continuous model but also provide more information on the description of nanoscale phenomena. In particular, MD results point out the importance of fluctuations when it comes to the description of the particular dynamics of nanosystems involving soft interfaces. This shows the need to improve continuous models by complementing them with a molecular approach for a better accuracy.

Sorption pH dependance of strontium/calcium by sodium nonatitanate.

Sodium nonatitanate powder is a layered material containing some potential exchangeable sodium ions between layers. In this work, sorption mechanism of this material has been studied and modeled at the solid-liquid interface. In particular, the ion-exchange mechanism is up to now not entirely known and especially the role of the pH on sorption properties. To investigate this latter, the solid is first equilibrated with inert acidic and base (nitric acid and triethylamine) for which the co-ions nitrate and triethylammonium do not penetrate the solid. The exchange between proton or divalent ions (strontium or calcium), and the sodium initially located in the sodium nonatitanate, is characterized through capillary ionic chromatography and conductivity experiments. To understand and explain the sorption properties, we modeled the equilibrium constant of different exchange reactions as a function of the solution pH. The equilibrium constants of the strontium/sodium and the calcium/sodium exchange have been obtained. We have shown the important role of the pH on the sorption rate of the strontium and moreover the hydrolysis rate of the sodium nonatitanate is calculated. We found that one eighth of sodium is spontaneously hydrolysed in aqueous phase whereas seven-eighths are exchanged by different divalent cations (strontium or calcium). Strontium and calcium exhibit similar exchange curves and competition with the proton adsorbed is modeled with global equilibrium constant. The prediction is in agreement with the conductivity experiments and the global extraction isotherms.

A predictive model of reverse micelles solubilizing water for solvent extraction.

Herein, a minimal model for the common case of W/O solubilization of badly soluble compounds present in an excess phase by reverse micellar aggregates in chemical equilibrium with its single compounds is introduced. A simple model of such liquid-liquid extractions is crucial for obtaining predictive parameter for the modelling of nuclear waste management and hydrometallurgic recycling strategies. The standard Gibbs free energy of aggregation and the concentration of the corresponding aggregate is calculated within a multiple-equilibria approach for a set of aggregate compositions of solute and amphiphilic extractant molecules. This minimal model provides potential surfaces estimating the stability of different aggregate compositions with 6.2kJmol(-1) as a generalized bending constant. The complete concentrations of free and aggregated extractant species as well as the favored aggregation numbers, the polydispersity, the activity of the organic solvent, and the critical concentrations are captured by this thermodynamic model. An increase of the apparent critical micelle concentration for an increasing solute content in the aqueous phase is detected by this method.

Ion-specific adsorption and electroosmosis in charged amorphous porous silica.

Monovalent and divalent aqueous electrolytes confined in negatively charged porous silica are studied by means of molecular simulations including free energy calculations. Owing to the strong cation adsorption at the surface, surface charge overcompensation (overscreening) occurs which leads to an effective positive surface next to the Stern layer, followed by a negatively charged diffuse layer. A simple Poisson-Boltzmann model in which the single-ion potential of mean force is introduced is shown to capture the most prominent features of ion density profiles near an amorphous silica surface. Nevertheless, due to its mean-field nature, which fails to account for correlations, this simple model does not predict overscreening corresponding to charge inversion at the surface. Such an overscreening drastically affects the transport of confined electrolytes as it leads to flow reversal when subjected to an electric field. A simple continuum theory is shown to capture how the electro-osmotic flow is affected by overscreening and by the apparent enhanced viscosity of the confined electrolytes. Comparison with available experimental data is discussed, as well as the implications of these phenomena for ζ-potential measurements.

Strontium selectivity in sodium nonatitanate Na 4Ti9O20·xH2O.

We study the extraction of strontium by sodium nonatitanate powder from nitrate strontium and acetate sodium mixture. Experiments show that adsorption is quantitative. The excess Gibbs free energy has been modeled by various models (ideal, 2D Coulomb, regular solution model) for the solid phase. We find that the free energy of the solid phase is controlled by short-range interactions rather than long-ranged Coulombic forces. The selectivity is the consequence of a competition between the liquid and solid phases: both phases prefer strontium rather than sodium but the solid contribution is predominant.

Luminescence of trivalent lanthanide ions excited by single-bubble and multibubble cavitations.

This article focuses on the possibility of exciting some lanthanides (Ce(3+), Tb(3+), Gd(3+), and Eu(3+)) by ultrasound in aqueous solutions. Depending on the lanthanide ions and on the acoustic cavitation conditions (single-bubble or multibubble systems), the excitation mechanism is shown to be photoexcitation (e.g., for Ce(3+)) or collision-induced excitation (e.g., for Tb(3+)). The sonoluminescence of Tb(3+) is studied in detail at various ultrasonic frequencies, allowing quantification of the amount of quenching. The latter is much stronger in sonoluminescence than in photoluminescence due to the particular properties of acoustic cavitation. Complexation with citrate ions enhances manifold sonoluminescence of lanthanides due to reduction of intra- and inner-molecular quenching.

The origin of isotope effects in sonoluminescence spectra of heavy and light water.

Bubble and peak: The isotope effects in the sonoluminescence spectra of light and heavy water under ultrasound indicate the formation of a non-equilibrium plasma inside the collapsing cavitation bubbles. The picture demonstrates the active cavitation zones in water at 204 kHz.

Nonequilibrium vibrational excitation of OH radicals generated during multibubble cavitation in water.

The sonoluminescence (SL) spectra of OH(A(2)Σ(+)) excited state produced during the sonolysis of water sparged with argon were measured and analyzed at various ultrasonic frequencies (20, 204, 362, 609, and 1057 kHz) in order to determine the intrabubble conditions created by multibubble cavitation. The relative populations of the OH(A(2)Σ(+)) v' = 1-4 vibrational states as well as the vibronic temperatures (T(v), T(e)) have been calculated after deconvolution of the SL spectra. The results of this study provide evidence for nonequilibrium plasma formation during sonolysis of water in the presence of argon. At low ultrasonic frequency (20 kHz), a weakly excited plasma with Brau vibrational distribution is formed (T(e) ~ 0.7 eV and T(v) ~ 5000 K). By contrast, at high-frequency ultrasound, the plasma inside the collapsing bubbles exhibits Treanor behavior typical for strong vibrational excitation. The T(e) and T(v) values increase with ultrasonic frequency, reaching T(e) ~ 1 eV and T(v) ~ 9800 K at 1057 kHz.

Hydrophobic transition in porous amorphous silica.

Realistic models of amorphous silica surfaces with different silanol densities are built using Monte Carlo annealing. Water-silica interfaces are characterized by their energy interaction maps, adsorption isotherms, self-diffusion coefficients, and Poiseuille flows. A hydrophilic to hydrophobic transition appears as the surface becomes purely siliceous. These results imply significant consequences for the description of surfaces. First, realistic models are required for amorphous silica interfaces. Second, experimental amorphous silica hydrophilicity is attributed to charged or uncharged defects, and not to amorphousness. In addition, autoirradiation in nuclear waste glass releases hydrogen atoms from silanol groups and can induce such a transition.

Stability and instability of the isoelectronic UO2(2+) and PaO2+ actinyl oxo-cations in aqueous solution from density functional theory based molecular dynamics.

In this work, Pa(V) monocations have been studied in liquid water by means of density functional theory (DFT) based molecular dynamic simulations (CPMD) and compared with their U(VI) isoelectronic counterparts to understand the peculiar chemical behavior of Pa(V) in aqueous solution. Four different Pa(V) monocationic isomers appear to be stable in liquid water from our simulations: [PaO(2)(H(2)O)(5)](+)(aq), [Pa(OH)(4)(H(2)O)(2)](+)(aq), [PaO(OH)(2)(H(2)O)(4)](+)(aq), and [Pa(OH)(4)(H(2)O)(3)](+)(aq). On the other hand, in the case of U(VI) only the uranyl, [UO(2)(H(2)O)(5)](2)(+)(aq), is stable. The other species containing hydroxyl groups replacing one or two oxo bonds are readily converted to uranyl. The Pa-OH bond is stable, while it is suddenly broken in U-OH. This makes possible the formation of a broad variety of Pa(V) species in water and participates to its unique chemical behavior in aqueous solution. Further, the two actinyl oxocations in water are different in the ability of the oxygen atoms to form stable and extended H-bond networks for Pa(V) contrary to U(VI). In particular, protactinyl is found to have between 2 and 3 hydrogen bonds per oxygen atom while uranyl has between zero and one.

Infrared spectroscopy of dioxouranium(V) complexes with solvent molecules: effect of reduction.

UO(2) (+)-solvent complexes having the general formula [UO(2)(ROH)](+) (R=H, CH(3), C(2)H(5), and n-C(3)H(7)) are formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they are isolated by mass-to-charge ratio, and then photofragmented using a free-electron laser scanning through the 10 mum region of the infrared spectrum. Asymmetric O=U=O stretching frequencies (nu(3)) are measured over a very small range [from approximately 953 cm(-1) for H(2)O to approximately 944 cm(-1) for n-propanol (n-PrOH)] for all four complexes, indicating that the nature of the alkyl group does not greatly affect the metal centre. The nu(3) values generally decrease with increasing nucleophilicity of the solvent, except for the methanol (MeOH)-containing complex, which has a measured nu(3) value equal to that of the n-PrOH-containing complex. The nu(3) frequency values for these U(V) complexes are about 20 cm(-1) lower than those measured for isoelectronic U(VI) ion-pair species containing analogous alkoxides. nu(3) values for the U(V) complexes are comparable to those for the anionic [UO(2)(NO(3))(3)](-) complex, and 40-70 cm(-1) lower than previously reported values for ligated uranyl(VI) dication complexes. The lower frequency is attributed to weakening of the O=U=O bonds by repulsion related to reduction of the U metal centre, which increases electron density in the antibonding pi* orbitals of the uranyl moiety. Computational modelling of the nu(3) frequencies using the B3LYP and PBE functionals is in good agreement with the IRMPD measurements, in that the calculated values fall in a very small range and are within a few cm(-1) of measurements. The values generated using the LDA functional are slightly higher and substantially overestimate the trends. Subtleties in the trend in nu(3) frequencies for the H(2)O-MeOH-EtOH-n-PrOH series are not reproduced by the calculations, specifically for the MeOH complex, which has a lower than expected value.

Infrared spectroscopy of discrete uranyl anion complexes.

The Free-Electron Laser for Infrared Experiments (FELIX) was used to study the wavelength-resolved multiple photon photodissociation of discrete, gas-phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands and are comparable to solution-phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm(-1) higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.