Debye-Hückel theory for interfacial geometries

The Debye-Hückel theory for bulk electrolyte solutions is generalized to planar interfacial geometries, including screening effects due to mobile salt ions which are confined to the interface and solutions with in general different salt concentrations and dielectric constants on the two sides of the interface. We calculate the general Debye-Hückel interaction between fixed test charges, and analyze a number of relevant special cases as applicable to charged colloids and charged polymers. Salty interfaces, which are experimentally realized by monolayers or bilayers made of cationic and anionic surfactants or lipids, exert a strong attraction on charged particles of either sign at large separations from the interface; at short distances image-charge repulsion sets in. Likewise, the effective interactions between charged particles are strongly modified in the neighborhood of such a salty interface. On the other hand, charged particles which are immersed in a salt solution are repelled from the air (or a substrate) interface, and the interaction between two charges decays algebraically close to such an interface. These general results have experimentally measurable consequences for the adsorption of charged colloids or charged polymers at monolayers, solid substrates, and interfaces.     

Interaction of surface plasmons with fluxes of charged particles crossing the interface between two media

Surface plasmon instability appearing during the interaction of plasmons with a flux of charged particles crossing the interface between media with different electromagnetic properties is predicted. The conditions under which instability appears are determined and the increments are found. The influence of the potential barrier at the interface on the interaction of surface plasmons with charged particles is investigated.     

Capillary freezing or complete wetting of hard spheres in a planar hard slit?

Extensive simulations of a hard sphere fluid confined between two planar hard walls show the onset of crystalline layers at the walls at about 98.3% of bulk crystallization density rho(f) independent of the wall separations L(z), and is, hence, a single wall phenomenon. As the bulk density far from the wall rho(b) increases, the thickness of the crystalline film appears to increase logarithmically, with (rho(f)-rho(b)) indicating complete wetting by the hard sphere crystal of the wall-fluid interface. Increasing rho(b) further, we observe a jump in the adsorption which depends on L(z) and corresponds to capillary freezing. The formation of crystalline layers below bulk crystallization, the logarithmic growth of the crystalline film, its independence of L(z), and its clear distinction from capillary freezing lend strong evidence for complete wetting by the hard sphere crystal at the wall-fluid interface.     

A hidden local symmetry approach to rho-meson photoproduction

We study the photoproduction of r \rho -mesons in a model of hidden local symmetry. For this purpose, the r \rho -meson is introduced as a hidden-gauge boson in a non-linear sigma model. For charged r \rho -meson photoproduction, the model takes into account the r \rho -meson magnetic moments from the three-point vertex in the kinetic terms. We show that the magnetic interaction of the charged r \rho -meson has a significant effect on the total cross-sections through the r \rho -meson exchange process, which is proportional to the energy of the photon. The t -channel dominance may be used for the study of structures of various unstable particles.     

Ellipsoidal particles at fluid interfaces

For partially wetting, ellipsoidal colloids trapped at a fluid interface, their effective, interface-mediated interactions of capillary and fluctuation-induced type are analyzed. For contact angles different from 90( degrees ) , static interface deformations arise which lead to anisotropic capillary forces that are substantial already for micrometer-sized particles. The capillary problem is solved using an efficient perturbative treatment which allows a fast determination of the capillary interaction for all distances between and orientations of two particles. Besides static capillary forces, fluctuation-induced forces caused by thermally excited capillary waves arise at fluid interfaces. For the specific choice of a spatially fixed three-phase contact line, the asymptotic behavior of the fluctuation-induced force is determined analytically for both the close-distance and the long-distance regime and compared to numerical solutions.     

Measurement of long-range repulsive forces between charged particles at an oil-water interface

Using a laser tweezers method, we have determined the long-range repulsive force as a function of separation between two charged, spherical polystyrene particles (2.7 microm diameter) present at a nonpolar oil-water interface. At large separations (6 to 12 microm between particle centers) the force is found to decay with distance to the power -4 and is insensitive to the ionic strength of the aqueous phase. The results are consistent with a model in which the repulsion arises primarily from the presence of a very small residual electric charge at the particle-oil interface. This charge corresponds to a fractional dissociation of the total ionizable (sulfate) groups present at the particle-oil surface of approximately 3 x 10(-4).     

Some effects of the electrostatic interaction of water drops in the atmosphere

The electric field at the surface of two conducting spherical charged particles and their interaction force are calculated. It is shown that as particles carrying like charge approach each other, the force changes sign and becomes attractive. The case where the charge on each particle varies as the square of its radius is an exception (repulsion at any distance between the particles). Self-similar asymptotic solutions for the interaction force and energy are found for particles of identical size. For a pair of charged water drops falling simultaneously in the atmosphere, a numerical simulation shows that a drop formed by coalescence of the pair may be subject to the Rayleigh instability. Zh. Tekh. Fiz. 69, 12–17 (December 1999)     

Diffusion transport of negative ions through the interface between cryogenic liquids

A theory of electron bubble transport through the interface between cryogenic liquids is developed based on a new approach to calculating the potential of interaction of a bubble with the interface. The theory is in good agreement with experiments on the electric-field dependence of the potential barrier near the interface between liquid ⁴He, ³He, and vacuum, as well as at the interface between ³He and ⁴He saturated solutions. It is found that the interaction potential dependence on the distance between the electron bubble and the interface is isotopically invariant to three versions of such an interface. The dependence of the lifetime of negative ions in ⁴He and ³He on the temperature and electric field has been determined using the Kramers theory.     

Ordered droplet structures at the liquid crystal surface and elastic-capillary colloidal interactions

We demonstrate a variety of ordered patterns, including hexagonal structures and chains, formed by colloidal particles (droplets) at the free surface of a nematic liquid crystal (LC). The surface placement introduces a new type of particle interaction as compared to particles entirely in the LC bulk. Namely, director deformations caused by the particles lead to distortions of the interface and thus to capillary attraction. The elastic-capillary coupling is strong enough to remain relevant even at the micron-scale when its buoyancy-capillary counterpart becomes irrelevant.     

Effective interactions of colloids on nematic films

The elastic and capillary interactions between a pair of colloidal particles trapped on top of a nematic film are studied theoretically for large separations d. The elastic interaction is repulsive and of quadrupolar type, varying as d^-5. For macroscopically thick films, the capillary interaction is likewise repulsive and proportional to d^-5 as a consequence of mechanical isolation of the system comprised of the colloids and the interface. A finite film thickness introduces a nonvanishing force on the system (exerted by the substrate supporting the film) leading to logarithmically varying capillary attractions. However, their strength turns out to be too small to be of importance for the recently observed pattern formation of colloidal droplets on nematic films.     

Coagulation of charged microparticles in neutral gas and charge-induced gel transitions

Coagulation of charged particles was studied using the mean-field Smoluchowski equation. The coagulation equation was generalized for the case of a conserved system of charged particles. It was shown that runaway cluster growth (gelation) solutions exist if the charge-dipole (induced) interaction of clusters is included. When clusters are in thermal equilibrium with the ambient gas, the charge-dipole interaction dramatically enhances the aggregation process and considerably increases the likelihood of a gelation transition.     

Capillary interactions between anisotropic colloidal particles

We report on the behavior of micron-sized prolate ellipsoids trapped at an oil-water interface. The particles experience strong, anisotropic, and long-ranged attractive capillary interactions which greatly exceed the thermal energy k(B)T. Depending on surface chemistry, the particles aggregate into open structures or chains. Using video microscopy, we extract the pair interaction potential between ellipsoids and show it exhibits a power law behavior over the length scales probed. Our observations can be explained using recent calculations, if we describe the interfacial ellipsoids as capillary quadrupoles.     

Quasi-steady-state modeling of dendritic growth

A new method of the moving-boundary problem analysis is developed. After proposed coordinate transformation, the quasi-steady-state differential equation was reduced to equivalent Laplace equation. Transformed boundary conditions of a rescaled field distribution reflect the presence of rate-dependent sources on interface. Taking into account the local rate-dependence of the Neumann's boundary conditions, non-equilibrium pattern formation was considered. The problem of dendrite fractal growth was reduced to one of interaction of conformal to tips charged particles. Conditions of the quasi-steady growth and the recurrence formula for k-order dendrite spacing were derived. Theoretically obtained scaling laws for interface shape, dendrite spacing, critical sidebranch distance are confirmed by available experimental data.     

On the possibility of corona-discharge ignition in the vicinity of a weakly charged drop executing nonlinear vibrations

An analytic expression for the electric-field strength in the vicinity of a charged drop of an electrically conducting liquid is obtained for the case where the initial shape of the drop executing nonlinear vibrations is specified by a virtual excitation of an arbitrary single mode of capillary vibrations. It turns out that, even at small charges (such that the Rayleigh parameter for the drop is equal to one-tenth of the critical value associated with stability against the intrinsic charge), the electric-field strength at the drop surface in the case of an initial excitation of one of high modes is sufficient for the ignition of a corona discharge.     

Debye-Hückel theory for slab geometries

The electrostatic interaction of charged particles through or at a low-dielectric slab, such as a lipid bilayer immersed in water or a self-assembled monolayer (SAM) on a metal substrate, is considered theoretically in the presence of salt within the Gaussian approximation using a generalized Green's formalism. A number of separate situations are discussed: i) The presence of a low-dielectric slab leads to pronounced interactions of a single charge with the slab via the formation of polarization surface charges. For SAMs on metal substrates, there is an intricate crossover from image-charge attraction to the metal substrate (for large distances) to image-charge repulsion from the SAM (for small distances) with a stable minimum at a distance of roughly 20 times the thickness of the hydrophobic film. For bilayers in water, the interaction of a single charge is always repulsive. ii) The surface potential of a SAM is calculated for the case when the hydrophobic layer contains dipole moments, which might explain the recently observed long-ranged repulsion of hydrophobic scanning tips from PEG-terminated SAMs on gold. iii) The interaction between charged particles through the bilayer is weakened. Oppositely charged particles still attract each other through the membrane. The free-energy minimum occurs as a result of the competition between self-repulsion from the slab and interparticle attraction and is located at a separation from the membrane surface which equals 15 times the membrane thickness. iv) Surface charges on the two surfaces of a bilayer attract each other through the bilayer unless the surface charge densities are the same, even if the signs are the same. v) All these effects are strongly influenced by the presence of salt. Received 25 January 2000     

Parametric buildup of the instability of a charged flat liquid surface imposed on Kelvin-Helmholtz instability

The instability of capillary gravitational waves that is developed at the charged flat interface between media is studied for the case when the upper medium moves parallel to the interface with a velocity that has constant and time-dependent components. It is shown that the Mathieu-Hill equation, describing the temporal evolution of the capillary wave amplitudes in such a system, has unstable solutions at those values of physical parameters (electric field strength and wind velocity) meeting the conditions for Saint Elmo fire initiation in the atmosphere.     

Electron Spin Resonance Study on the Photoinduced Electron Transfer in Chlorophyll a in Reconstituted Lipid Bilayer Vesicles

Abstract  

The photoinduced electron transfer from chlorophyll a through the interface of positively charged dioctadecyltrimethylammonium chloride (DODAC), neutral dipalmitoylphosphatidylcholine (DPPC) and negatively charged dihexadecylphosphate (DHP) headgroup of the lipid bilayers was studied. The photoinduced radicals were identified by electron spin resonance (ESR) and radical yields of chlorophyll a were determined by double integration of the ESR spectra. The formation of vesicles was identified indirectly by measuring change of the λ _max value of optical absorption spectrophotometer from diethyl ether solution to vesicle solutions, and observed directly with scanning and transmission electron microscopic images. The interaction distance between chlorophyll a and interface water (D₂O) determined by deuterium modulation depth with electron spin echo modulation (ESEM) showed a decreasing order DODAC > DPPC > DHP. The interface charge of each vesicle was determined with zeta potential measurement. The interface charge of the lipid bilayers affected the radical yields of chlorophyll a more critically than the interaction distance between chlorophyll a and interface water.     

A microscopic model of sequential resonant tunneling transport through weakly coupled superlattices

A microscopic model is developed for resonant tunneling transport in weakly coupled semiconductor superlattices in a constant external electric field. The model takes into account multiple subbands and electric-field dependence of scattering by acoustic and optical phonons, charged impurities, and interface roughness. The model is used as a basis for computing the resonant-tunneling profiles for structures with small size-quantization energies. The computed results are in good agreement with experiment. In structures of this type, an important role is played by electric-field dependence of scattering processes and the threshold behavior of elastic processes is strongly manifested. A substantial asymmetry is predicted not only for the first tunneling resonance, but also for higher order resonant tunneling processes.     

Collective dynamics of colloids at fluid interfaces

The evolution of an initially prepared distribution of micron-sized colloidal particles, trapped at a fluid interface and under the action of their mutual capillary attraction, is analyzed by using Brownian dynamics simulations. At a separation λ given by the capillary length of typically 1mm, the distance dependence of this attraction exhibits a crossover from a logarithmic decay, formally analogous to two-dimensional gravity, to an exponential decay. We discuss in detail the adaptation of a particle-mesh algorithm, as used in cosmological simulations to study structure formation due to gravitational collapse, to the present colloidal problem. These simulations confirm the predictions, as far as available, of a mean-field theory developed previously for this problem. The evolution is monitored by quantitative characteristics which are particularly sensitive to the formation of highly inhomogeneous structures. Upon increasing λ the dynamics shows a smooth transition from the spinodal decomposition expected for a simple fluid with short-ranged attraction to the self-gravitational collapse scenario.     

Transition from Kardar-Parisi-Zhang to tilted interface critical behavior in a solvable asymmetric avalanche model

We use a discrete-time formulation of the asymmetric avalanche process (ASAP) [Phys. Rev. Lett. 87, 084301 (2001)]] of p particles on a finite ring of N sites to obtain an exact expression for the average avalanche size as a function of toppling probabilities and particle density rho=p/N. By mapping the model onto driven interface problems, we find that the ASAP incorporates the annealed Kardar-Parizi-Zhang and quenched tilted interface dynamics for rhorho(c), respectively, with rho(c) being the critical density for given toppling probabilities and N--> infinity. We analyze the crossover between two regimes and show which parameters are relevant near the transition point.