Swelling behavior and viscoelasticity of ultrathin grafted hyaluronic acid films

In this paper we study the effect of monovalent and divalent ions on the swelling behavior and viscoelastic parameters of ultrathin layers of the natural polyelectrolyte hyaluronic acid covalently coupled to glass substrates. A colloidal probe technique is applied for this purpose based on latex beads, hovering over the polymer cushion. By analyzing the vertical Brownian motion of these beads with reflection interference contrast microscopy (RICM) we determined the equilibrium layer thickness (with 3 nm vertical resolution), the interfacial interaction potential, and the characteristic mesh size limiting the hydrodynamic flow within the polyelectrolyte film as a function of the ionic strength. The experimental results are interpreted in terms of three different theoretical models: the polyelectrolyte brush approximation of Pincus [#!ref1!#], a modified polyelectrolyte brush approximation in the high salt concentration limit of Ross and Pincus [#!ref2!#] and the simple scaling approximation for neutral adsorbed polymers of de Gennes [#!ref3!#]. Within experimental error all of these different models fit our experimental data and yield comparable results for the equilibrium layer thickness. Moreover we determine a thickness dependent, effective surface coverage from both brush models. The hydrodynamic properties of the films are interpreted in terms of the Brinkmann model of elastic porous media by assuming an effective mesh size, which depends linearly on the Debye screening length. The salt induced condensation of the polyelectrolyte films can be described microscopically in terms of a progressive contraction of the mesh size with increasing salt concentration. Received 10 September 1998 and Received in final form 30 November 1998     

Spreading and two-dimensional mobility of long-chain alkanes at solid/gas interfaces

Long-chain n alkanes on solid surfaces can form partially wetting liquid alkane droplets coexisting with solid multilayer terraces. We propose a diffusivelike alkane flow between terrace edge and droplet perimeter through a molecularly thin "precursorlike" film. Depending on the (uniform!) sample temperature, either droplet or terrace edge are not in thermodynamic equilibrium. This leads to a chemical potential gradient, which drives the reversible alkane flow. The gradient can be adjusted and calculated independently from the phenomenological diffusion coefficient.     

Water droplets in a spherically confined nematic solvent: A numerical investigation

Recently, it was observed that water droplets suspended in a nematic liquid crystal form linear chains [Poulin et al., Science 275, 1770 (1997)]. The chaining occurs, e.g., in a large nematic drop with homeotropic boundary conditions at all the surfaces. Between each pair of water droplets a point defect in the liquid crystalline order was found in accordance with topological constraints. This point defect causes a repulsion between the water droplets. In our numerical investigation we limit ourselves to a chain of two droplets. For such a complex geometry we use the method of finite elements to minimize the Frank free energy. We confirm an experimental observation that the distance d of the point defect from the surface of a water droplet scales with the radius r of the droplet like .When the water droplets are moved apart, we find that the point defect does not stay in the middle between the droplets, but rather forms a dipole with one of them. This confirms a theoretical model for the chaining. Analogies to a second order phase transition are drawn. We also find the dipole when one water droplet is suspended in a bipolar nematic drop with two boojums, i.e., surface defects at the outer boundary. Finally, we present a configuration where two droplets repel each other without a defect between them. Received 11 December 1998     

A kinetic model for droplet growth in the transition regime

A variant of the moment expansion method, used in an earlier paper to describe the flow of a gas toward an absorbing sphere, is applied to a more realistic model of a droplet condensing from a supersaturated vapor. In the simplest version a spherical droplet absorbs all incoming vapor molecules, but spontaneously emits molecules with a Maxwellian distribution at the droplet temperature and with the corresponding saturated vapor density. From a solution of the stationary linearized Boltzmann equation with these boundary conditions we obtain expressions for the heat and mass currents toward the sphere as a function of the supersaturation and the temperature difference between the droplet and the vapor at infinity. For small droplet radii the known free flow limit is obtained in a natural way. From the calculated expressions for the heat and mass current we derive evolution equations for the radius and temperature of the droplet. The temperature evolves more rapidly and can thus be eliminated adiabatically; the resulting growth curve for the radius shows a sharp transition from a kinetically controlled regime for small radii to a regime dominated by heat conduction for large radii. The effect of incomplete absorption at the surface is also studied. The actual calculations are carried out for Maxwell molecules, with parameters corresponding to argon at 0.65T _c and 100% supersaturation.     

Super lattice formation of an array of volatile wetting droplets

For an ordered array of critical volatile wetting droplets the formation of a super lattice by an Ostwald-ripening-like competition process is considered. The underlying diffusion problem is treated within a quasistatic approximation and to first order in the inverse droplets distance. The approach is rather general but a square lattice and a triangular lattice are studied explicitly. Dispersion relations for the super lattice growth of these arrays are calculated. Received 29 November 1999 and Received in final form 15 February 2000     

A model for ripple instabilities in granular media

We extend the model of surface granular flow proposed in [#!bcre!#] to account for the effect of an external `wind', which acts as to dislodge particles from the static bed, such that a stationary state of flowing grains is reached. We discuss in detail how this mechanism can be described in a phenomenological way, and show that a flat bed is linearly unstable against ripple formation in a certain region of parameter space. We focus in particular on the (realistic) case where the migration velocity of the instability is much smaller than the grains' velocity. In this limit, the full dispersion relation can be established. We relate the critical wave vector to the mean hopping length and to the ratio of the flight time to the `stick' time. We provide an intuitive interpretation of the instability. Received: 30 January 1998 / Revised: 12 May 1998 / Accepted: 8 June 1998     

A Model of Irradiance Distribution for a Directed Point Source in an Infinite Weakly Absorbing Turbid Medium

We propose simple models describing the irradiance distributions for a unidirectional point source in an infinite weakly absorbing turbid medium and also for a narrow light beam obliquely incident on the boundary of a semi-infinite turbid medium. These models involve the same optical parameters of the medium as the formulas of the diffusion approximation of radiation-transport theory. At the same time, the condition of weak anisotropy of the radiation field does not limit the applicability of our models.     

Adsorption of a Gaussian random copolymer chain at an interface

We consider the adsorption of an isolated, Gaussian, random, and quenched copolymer chain at an interface. We first propose a simple analytical method to obtain the adsorption/depletion transition, by averaging over the disorder the partition function instead of the free energy. The adsorption thresholds obtained by previous authors at a solid/liquid and at a liquid/liquid interface for multicopolymer chains can be rederived using this method. We also compare the adsorption thresholds obtained for bimodal and for Gaussian disorder; they only agree for small disorder. We focus on the specific case of an ideally flat asymmetric liquid/liquid interface, and consider the situation where the chain is composed of monomers of two different chemical species A and B. The replica method is developed for this case. We show that the Hartree approximation, coupled to a replica symmetry assumption, leads to the same adsorption thresholds as obtained from our general method. In order to describe the properties of the adsorbed (or depleted) chain, we develop a new approximation for long chains, within the framework of the replica theory. In most cases, the behavior of a random copolymer chain can be mapped onto that of a homopolymer chain at an asymmetric attractive interface. The values of the effective adsorption energy are different for a random and a periodic copolymer chain. Finally, we consider the case of uncorrelated annealed disorder. The behavior of an annealed chain can be mapped onto that of a homopolymer chain at an asymmetric non attractive interface; hence, an annealed chain cannot adsorb at an asymmetric interface. Received 21 January 1999     

A nonlinear model for aeolian sand ripples

Starting from the phenomenological model for sand ripple formation developed in [#!Bouchaud98!#], we proposed a new interpretation in the light of recent experiments. Furthermore, we derive, close to the threshold of ripple instability, a nonlinear equation for the spatio-temporal evolution of the sand bed profile, which to leading order has a quadratic nonlinearity. This equation is identical to that derived recently on the basis of geometry and conservation law [#!Csahok98!#]. Our derivation connects the coefficients of the nonlinear equation to the underlying physical mechanisms (reptation length...). This equation reveals ripple structures which then undergo a coarsening process, as observed in wind tunnel experiment. Small, fast moving ripples are absorbed by larger, slower forms resulting in a growth of the mean wavelength. Received 5 January 1999     

Piezoelectricity of chiral nematic elastomers

A molecular model of freely jointed chains of chiral monomers is developed to describe the piezoelectric effect in chiral nematic elastomers. The model, an extension of the neo-classical theory of nematic polymer networks, takes into account a chiral biasing of molecular alignment under shear which leads to induced polarisation if the monomers contain a transverse dipole moment. The resulting theory is fully non-linear in elastic deformations, in the spirit of ordinary rubber elasticity. The expansion to the highest order in small strains gives the three linear piezoelectric coefficients predicted by phenomenological models. Received 7 September 1998 and Received in final form 19 October 1998     

Fano-like coupling of collective and particle-hole excitations in Li metal

The dynamic structure factor of Li with [110] and 0.88 a.u. <q< 1.03 a.u., as measured with 1 eV resolution by means of synchrotron radiation based inelastic X-ray scattering spectroscopy (IXSS), exhibits, in the energy loss range between 3 and 12 eV, a fine structure, which appears as a resonance around 4 eV and an antiresonance around 8 eV, when the difference between the experimental -spectra with [110] and [111] is considered. In order to find out the origin of this fine structure we have interpreted recent TLDA (time dependent local density approximation) calculations of the Li- [#!ref12!#], which were based on the inversion of the full dielectric matrix, by utilizing a simple two-plasmon-band model. In this way the fine structure can be traced back to a Fano-like coupling of the discrete collective excitations (both the regular plasmon and the so-called zone-boundary collective states (ZBCS's)) and the particle-hole excitation continuum, mediated by the off-diagonal elements of the dielectric matrix, , where (1,1,0). Received: 29 December 1998 / Accepted: 16 March 1998     

The kinetic boundary layer around an absorbing sphere and the growth of small droplets

Deviations from the classical Smoluchowski expression for the growth rate of a droplet in a supersaturated vapor can be expected when the droplet radius is not large compared to the mean free path of a vapor molecule. The growth rate then depends significantly on the structure of the kinetic boundary layer around a sphere. We consider this kinetic boundary layer for a dilute system of Brownian particles. For this system a large class of boundary layer problems for a planar wall have been solved. We show how the spherical boundary layer can be treated by a perturbation expansion in the reciprocal droplet radius. In each order one has to solve a finite number ofplanar boundary layer problems. The first two corrections to the planar problem are calculated explicitly. For radii down to about two velocity persistence lengths (the analog of the mean free path for a Brownian particle) the successive approximations for the growth rate agree to within a few percent. A reasonable estimate of the growth rate for all radii can be obtained by extrapolating toward the exactly known value at zero radius. Kinetic boundary layer effects increase the time needed for growth from 0 to 10 (or 2 1/2) velocity persistence lengths by roughly 35% (or 175%).     

Corrections to the wave function and the hyperfine structure in exotic atoms

We present an analytical evaluation of radiative corrections in exotic atoms induced by the one-loop electronic vacuum polarization. We evaluate corrections to the energy levels, to the wave function (at the origin) and to the hyperfine structure. We treat all corrections analytically within a non-relativistic approximation. Agreement is found with a few available numerical results. The analytical treatment allows to determine the asymptotic forms of the corrections in the limit of a small atomic radius, which for the atomic systems considered corresponds to a large mass of the constituent particle as compared to the electron mass. The asymptotics can be verified using the effective charge approach. Received: 28 January 1998 / Accepted: 13 March 1998     

Anharmonic oscillators energies via artificial perturbation method

A new pseudoperturbative (artificial in nature) methodical proposal [#!ref15!#] is used to solve for Schr?dinger equation with a class of phenomenologically useful and methodically challenging anharmonic oscillator potentials . The effect of the [#!ref4!#,#!ref5!#] Padé approximant on the leading eigenenergy term is studied. Comparison with results from numerical (exact) and several eligible (approximation) methods is made. Received 2 July 1999 and Received in final form 18 November 1999     

Asymptotic analysis of wall modes in a flexible tube

The stability of wall modes in a flexible tube of radius R surrounded by a viscoelastic material in the region R < r < H R in the high Reynolds number limit is studied using asymptotic techniques. The fluid is a Newtonian fluid, while the wall material is modeled as an incompressible visco-elastic solid. In the limit of high Reynolds number, the vorticity of the wall modes is confined to a region of thickness in the fluid near the wall of the tube, where the small parameter , and the Reynolds number is , and are the fluid density and viscosity, and V is the maximum fluid velocity. The regime is considered in the asymptotic analysis, where G is the shear modulus of the wall material. In this limit, the ratio of the normal stress and normal displacement in the wall, , is only a function of H and scaled wave number . There are multiple solutions for the growth rate which depend on the parameter .In the limit , which is equivalent to using a zero normal stress boundary condition for the fluid, all the roots have negative real parts, indicating that the wall modes are stable. In the limit , which corresponds to the flow in a rigid tube, the stable roots of previous studies on the flow in a rigid tube are recovered. In addition, there is one root in the limit which does not reduce to any of the rigid tube solutions determined previously. The decay rate of this solution decreases proportional to in the limit , and the frequency increases proportional to . Received: 5 November 1997 / Revised: 10 March 1998 / Accepted: 29 April 1998     

Diffusive mobility of fractal aggregates over the entire Knudsen number range

We determine the effective mobility radius for fractal aggregate particles. Our method is to use static light scattering to measure the radius of gyration R(g) of the aggregates, and dynamic light scattering to measure the diffusion coefficient hence the mobility radius R(m). The range of our results can be specified by the Knudsen number Kn, which is the mean free path of the medium molecules divided by the radius of the aggregate. Our results apply to the entire range of Kn from the continuum limit (Kn=0) to the free molecular limit (Kn>1). In the continuum regime we find R(m)/R(g)=0.97+/-0.05 when the aggregate fractal dimension is D(f) approximately 2.15, and 0.70+/-0.05 when D(f) approximately 1.75. The latter result is independent of Kn for Kn < or approximately 1.3. The free molecular mobility goes as R(m)=aN(0.44+/-0.03), where a is the monomer radius and N is the number of monomers per aggregate. Since R(g) approximately aN(1/D(f)), R(m)/R(g) is not a constant when Kn is large. We find for all Kn that the functionality of R(m)/R(g) must always begin with the correct N-->1 limit, and this affects experimental observation.     

Reaction kinetics in polymer melts

We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant k after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi [#!doi:inter2!#], de Gennes [#!gennes:polreactionsiandii!#], and Friedman and O'Shaughnessy [#!ben:interdil_all_aip!#], to arbitrary initial reactive group density n₀ and local chemical reactivity Q. Simple mean field (MF) kinetics apply at short times, .For high Q, a transition occurs to diffusion-controlled (DC) kinetics with (where x_t is rms monomer displacement in time t) leading to a density decay . If n₀ exceeds the chain overlap threshold, this behavior is followed by a regime where during which k has the same power law dependence in time, , but possibly different numerical coefficient. For unentangled melts this gives while for entangled cases one or more of the successive regimes ,t ^-3/8 and t ^-3/4 may be realized depending on the magnitudes of Q and n₀. Kinetics at times longer than the longest polymer relaxation time are always MF. If a DC regime has developed before then the long time rate constant is where R is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis. Received: 2 June 1998 / Revised: 9 July 1998 / Accepted: 10 July 1998     

Optimization of EUV radiation yield from laser-produced plasma

We optimize the conversion of laser energy into extreme ultraviolet (EUV) radiation by tailoring the laser parameters for a laser-produced plasma generated from 20 μm diameter water droplets. It is shown that mass-limited targets require careful adaption of laser-pulse energy and laser-pulse duration separately, rather than laser intensity, which seems to be adequate for bulk targets. The optimal pulse duration scales with the droplet radius, and the optimal pulse energy with the droplet volume. With optimized parameters, we obtain a conversion efficiency of 0.23% in 4π and 2.5% bandwidth for 13 nm radiation, the future EUV lithography light. Received: 16 July 2001 / Revised version: 25 September 2001 / Published online: 7 November 2001     

A theoretical spectroscopic study of single ammonia molecules adsorbed on the surface of fcc-type argon clusters. Surface effects on the ν 2 vibration-inversion mode

Ammonia monomers have been adsorbed on argon clusters at low temperature K by Rohmund and Huisken [#!frfh97!#] using the pick-up technique. They measured the spectrum of the NH₃ molecules in the region of the umbrella mode. Two broad bands centered around 970 and 1000 cm^-1 with finer details were observed. The authors attempted to interpret the obtained spectrum on the basis of the free rotation motions of the molecules. In this paper semi-empirical atom-atom potential energy calculations are performed for the ammonia monomer adsorbed on a rigid face-centered-cubic (fcc)-type surface of the argon cluster. In the equilibrium position of the rigid molecule on the cluster surface the orientational potential energy surface exhibits two quasi-equivalent minima separated by a potential barrier of about 100 cm^-1. The symmetry of the molecular vibration-inversion double-well potential is destroyed; the inversion motion is then forbidden in the ground state. On the basis of the two adsorption orientations, the vibrational frequency shifts are calculated and the obtained infrared bar-spectrum agrees with the experimental one. Received 6 April 1999 and Received in final form 19 July 1999