Coalescence in low-viscosity liquids

The expected universal dynamics associated with the initial stage of droplet coalescence are difficult to study visually due to the rapid motion of the liquid and the awkward viewing geometry. Here we employ an electrical method to study the coalescence of two inviscid droplets at early times. We measure the growth dynamics of the bridge connecting the two droplets and observe a new asymptotic regime inconsistent with previous theoretical predictions. The measurements are consistent with a model in which the two liquids coalesce with a slightly deformed interface.Comment: 4 pages and 4 figure

Thermodynamic behaviour and structural properties of an aqueous sodium chloride solution upon supercooling

We present the results of a molecular dynamics simulation study of thermodynamic and structural properties upon supercooling of a low concentration sodium chloride solution in TIP4P water and the comparison with the corresponding bulk quantities. We study the isotherms and the isochores for both the aqueous solution and bulk water. The comparison of the phase diagrams shows that thermodynamic properties of the solution are not merely shifted with respect to the bulk. Moreover, from the analysis of the thermodynamic curves, both the spinodal line and the temperatures of maximum density curve can be calculated. The spinodal line appears not to be influenced by the presence of ions at the chosen concentration, while the temperatures of maximum density curve displays both a mild shift in temperature and a shape modification with respect to bulk. Signatures of the presence of a liquid-liquid critical point are found in the aqueous solution. By analysing the water-ion radial distribution functions of the aqueous solution we observe that upon changing density, structural modifications appear close to the spinodal. For low temperatures additional modifications appear also for densities close to that corresponding to a low density configurational energy minimum.Comment: 10 pages, 13 figures, 2 tables. To be published in J. Chem. Phy

Non-mean-field theory of anomalously large double-layer capacitance

Mean-field theories claim that the capacitance of the double-layer formed at a metal/ionic conductor interface cannot be larger than that of the Helmholtz capacitor, whose width is equal to the radius of an ion. However, in some experiments the apparent width of the double-layer capacitor is substantially smaller. We propose an alternate, non-mean-field theory of the ionic double-layer to explain such large capacitance values. Our theory allows for the binding of discrete ions to their image charges in the metal, which results in the formation of interface dipoles. We focus primarily on the case where only small cations are mobile and other ions form an oppositely-charged background. In this case, at small temperature and zero applied voltage dipoles form a correlated liquid on both contacts. We show that at small voltages the capacitance of the double-layer is determined by the transfer of dipoles from one electrode to the other and is therefore limited only by the weak dipole-dipole repulsion between bound ions, so that the capacitance is very large. At large voltages the depletion of bound ions from one of the capacitor electrodes triggers a collapse of the capacitance to the much smaller mean-field value, as seen in experimental data. We test our analytical predictions with a Monte Carlo simulation and find good agreement. We further argue that our ``one-component plasma" model should work well for strongly asymmetric ion liquids. We believe that this work also suggests an improved theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about aqueous solutions adde

Measurements of the Casimir-Lifshitz force in fluids: the effect of electrostatic forces and Debye screening

In this work, we present detailed measurements of the Casimir-Lifshitz force between two gold surfaces (a sphere and a plate) immersed in ethanol and study the effect of residual electrostatic forces, which are dominated by static fields within the apparatus and can be reduced with proper shielding. Electrostatic forces are further reduced by Debye screening through the addition of salt ions to the liquid. Additionally, the salt leads to a reduction of the Casimir-Lifshitz force by screening the zero-frequency contribution to the force; however, the effect is small between gold surfaces at the measured separations and within experimental error. An improved calibration procedure is described and compared to previous methods. Finally, the experimental results are compared to Lifshitz's theory and found to be consistent for the materials used in the experiment.Comment: 11 figures. PRA in pres

Porous silicon formation and electropolishing

Electrochemical etching of silicon in hydrofluoride containing electrolytes leads to pore formation for low and to electropolishing for high applied current. The transition between pore formation and polishing is accompanied by a change of the valence of the electrochemical dissolution reaction. The local etching rate at the interface between the semiconductor and the electrolyte is determined by the local current density. We model the transport of reactants and reaction products and thus the current density in both, the semiconductor and the electrolyte. Basic features of the chemical reaction at the interface are summarized in law of mass action type boundary conditions for the transport equations at the interface. We investigate the linear stability of a planar and flat interface. Upon increasing the current density the stability flips either through a change of the valence of the dissolution reaction or by a nonlinear boundary conditions at the interface.Comment: 18 pages, 8 figure

Reaction-Diffusion Processes with Nonlinear Diffusion

We study reaction-diffusion processes with concentration-dependent diffusivity. First, we determine the decay of the concentration in the single-species and two-species diffusion-controlled annihilation processes. We then consider two natural inhomogeneous realizations. The two-species annihilation process is investigated in the situation when the reactants are initially separated, namely each species occupies a half space. In particular, we determine the growth law of the width of the reaction zone. The single-species annihilation process is studied in the situation when the spatially localized source drives the system toward the non-equilibrium steady state. Finally we investigate a dissolution process with a localized source of diffusing atoms which react with initially present immobile atoms forming immobile molecules.Comment: Figure and references added, final versio

Diffuse-Charge Dynamics in Electrochemical Systems

The response of a model micro-electrochemical system to a time-dependent applied voltage is analyzed. The article begins with a fresh historical review including electrochemistry, colloidal science, and microfluidics. The model problem consists of a symmetric binary electrolyte between parallel-plate, blocking electrodes which suddenly apply a voltage. Compact Stern layers on the electrodes are also taken into account. The Nernst-Planck-Poisson equations are first linearized and solved by Laplace transforms for small voltages, and numerical solutions are obtained for large voltages. The ``weakly nonlinear'' limit of thin double layers is then analyzed by matched asymptotic expansions in the small parameter $\epsilon = \lambda_D/L$, where $\lambda_D$ is the screening length and $L$ the electrode separation. At leading order, the system initially behaves like an RC circuit with a response time of $\lambda_D L / D$ (not $\lambda_D^2/D$), where $D$ is the ionic diffusivity, but nonlinearity violates this common picture and introduce multiple time scales. The charging process slows down, and neutral-salt adsorption by the diffuse part of the double layer couples to bulk diffusion at the time scale, $L^2/D$. In the ``strongly nonlinear'' regime (controlled by a dimensionless parameter resembling the Dukhin number), this effect produces bulk concentration gradients, and, at very large voltages, transient space charge. The article concludes with an overview of more general situations involving surface conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference

Orbital overlap effects in electron transfer reactions across a metal nanowire/electrolyte solution interface

In this paper, we report on calculations of the orbital overlap between Fe(III) and Cr(III) aquacomplexes and different electrode surfaces: Cu(111), Ag (111), Au(111), Pt(111), and corresponding monatomic wires. The electronic structure of the monocrystalline surfaces and nanowires are described in terms of the electronic spillover and density of electronic states at the Fermi level obtained from periodic density functional theory (DFT) calculations. The transmission coefficients (κ) characterizing the first stage of outer-sphere electron transfer for the reduction of aquacomplexes are calculated on the basis of Landau–Zener theory as a function of electrode–reactant separation; the electronic transmission coefficients for the [Cr(H2O)6]3+/2+ redox couple were found to be smaller than those for [Fe(H2O)6]3+/2+. Two different intervals can be clearly distinguished for Cu, Au and Pt: “a catalytic region”, where κ(wire) > κ(Me slab) and “an inhibition region”, where κ(wire) < κ(Me slab). A similar behavior exhibits the coupling constant estimated for a hydrogen atom adsorbed at the Au(111) surface and the Au monatomic wire. These effects originate from some specific features of electronic density profile for metal nanowires: at short distances the electronic density of nanowires is higher compared with the (111) metal surfaces, while at larger separations it decreases more sharply.Fil: Nazmutdinov, Renat R.. Kazan National Research Technological University; RusiaFil: Berezin, Alexander S.. Kazan National Research Technological University; RusiaFil: Soldano, Germán. Universitat Ulm; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Schmickler, Wolfgang. Universitat Ulm; Alemani