Van der Waals interactions across stratified media

Working at the Lifshitz level, we investigate the van der Waals interactions across a series of layers with a periodic motif. We derive the complete form of the van der Waals interaction as an explicit function of the number of periodic layers. We then compare our result with an approximation based on an anisotropic-continuum representation of the stratified medium. Satisfactory agreement between discrete-layer and continuum models is reached only for thicknesses of ten or more layers.Comment: 9 pages and 4 figure

Elastic moduli renormalization in self interacting stretchable polyelectrolytes

We study the effect of intersegment interactions on the effective bending and stretching moduli of a semiflexible polymer chain with a finite stretching modulus. For an interaction potential of a screened Debye-H\" uckel type renormalization of the stretching modulus is derived on the same level of approximation as the celebrated Odijk-Skolnick-Fixman result for the bending modulus. The presence of mesoscopic intersegment interaction potentials couples the bending and stretching moduli in a manner different from that predicted by the macroscopic elasticity theory. We advocate a fundamental change in the perspective regarding the dependence of elastic moduli of a flexible polyelectrolyte on the ionic conditions: stretchability. Not only are the persistence length as well as the stretching modulus dependent on the salt conditions in the solution, they are fundamentally coupled via the mesoscopic intersegment interaction potential. The theory presented here compares favorably with recent experiments on DNA bending and stretching.Comment: 12 pages, 3 figure

Three-body Casimir effects and non-monotonic forces

Casimir interactions are not pair-wise additive. This property leads to collective effects that we study for a pair of objects near a conducting wall. We employ a scattering approach to compute the interaction in terms of fluctuating multipoles. The wall can lead to a non-monotonic force between the objects. For two atoms with anisotropic electric and magnetic dipole polarizabilities we demonstrate that this non-monotonic effect results from a competition between two- and three body interactions. By including higher order multipoles we obtain the force between two macroscopic metallic spheres for a wide range of sphere separations and distances to the wall.Comment: 4 pages, 4 figure

Ion Induced Lamellar-Lamellar Phase Transition in Charged Surfactant Systems

We propose a model for the liquid-liquid phase transition observed in osmotic pressure measurements of certain charged lamellae-forming amphiphiles. The model free energy combines mean-field electrostatic and phenomenological non-electrostatic interactions, while the number of dissociated counterions is treated as a variable degree of freedom that is determined self-consistently. The model, therefore, joins two well-known theories: the Poisson-Boltzmann theory for ionic solutions between charged lamellae, and Langmuir-Frumkin-Davies adsorption isotherm modified to account for charged adsorbing species. Minimizing the appropriate free energy for each interlamellar spacing, we find the ionic density profiles and the resulting osmotic pressure. While in the simple Poisson-Boltzmann theory the osmotic pressure isotherms are always smooth, we observe a discontinuous liquid-liquid phase transition when Poisson-Boltzmann theory is self-consistently augmented by Langmuir-Frumkin-Davies adsorption. This phase transition depends on the area per amphiphilic headgroup, as well as on non-electrostatic interactions of the counterions with the lamellae, and interactions between counterion-bound and counterion-dissociated surfactants. Coupling lateral phase transition in the bilayer plane with electrostatic interactions in the bulk, our results offer a qualitative explanation for the existence of the phase-transition of DDABr (didodecyldimethylammonium bromide), but its apparent absence for the chloride and the iodide homologues. More quantitative comparisons with experiment require better understanding of the microscopic basis of the phenomenological model parameters.Comment: 14 pages, 9 figure

Charge Fluctuation Forces Between Stiff Polyelectrolytes in Salt Solution: Pairwise Summability Re-examined

We formulate low-frequency charge-fluctuation forces between charged cylinders - parallel or skewed - in salt solution: forces from dipolar van der Waals fluctuations and those from the correlated monopolar fluctuations of mobile ions. At high salt concentrations forces are exponentially screened. In low-salt solutions dipolar energies go as $R^{-5}$ or $R^{-4}$; monopolar energies vary as $R^{-1}$ or $\ln{R}$, where $R$ is the minimal separation between cylinders. However, pairwise summability of rod-rod forces is easily violated in low-salt conditions. Perhaps the most important result is not the derivation of pair potentials but rather the demonstration that some of these expressions may not be used for the very problems that originally motivated their derivation.Comment: 8 pages and 1 fig in ps forma

Bond Orientational Order, Molecular Motion and Free Energy of High Density DNA Mesophases

By equilibrating condensed DNA arrays against reservoirs of known osmotic stress and examining them with several structural probes, it has been possible to achieve a detailed thermodynamic and structural characterization of the change between two distinct regions on the liquid crystalline phase digram: a higher-density hexagonally packed region with long-range bond orientational order in the plane perpendicular to the average molecular direction; and a lower-density cholesteric region with fluid-like positional order. X-rays scattering on highly ordered DNA arrays at high density and with the helical axis oriented parallel to the incoming beam showed a six-fold azimuthal modulation of the first order diffraction peak that reflects the macroscopic bond-orientational order. Transition to the less-dense cholesteric phase through osmotically controlled swelling shows the loss of this bond orientational order that had been expected from the change in optical birefringence patterns and that is consistent with a rapid onset of molecular positional disorder. This change in motion was previously inferred from intermolecular force measurements and is now confirmed by $\rm ^{31}P$ NMR. Controlled reversible swelling and compaction under osmotic stress, spanning a range of densities between $\sim 120$ mg/ml to $\sim 600$ mg/ml, allows measurement of the free energy changes throughout each phase and at the phase transition, essential information for theories of liquid-crystalline states.Comment: 14 pages, 3 figures in gif format available at http://abulafia.mgsl.dcrt.nih.gov/pics.html E-mail: [email protected]

Recursion relations for generalized Fresnel coefficients: Casimir force in a planar cavity

We emphasize and demonstrate that, besides using the usual recursion relations involving successive layers, generalized Fresnel coefficients of a multilayer can equivalently be calculated using the recursion relations involving stacks of layers, as introduced some time ago [M. S. Tomas, Phys. Rev. A 51, 2545 (1995)]. Moreover, since the definition of the generalized Fresnel coefficients employed does not imply properties of the stacks, these nonstandard recursion relations can be used to calculate Fresnel coefficients not only for local systems but also for a general multilayer consisting of various types (local, nonlocal, inhomogeneous etc.) of layers. Their utility is illustrated by deriving a few simple algorithms for calculating the reflectivity of a Bragg mirror and extending the formula for the Casimir force in a planar cavity to arbitrary media.Comment: 5 pages, 2 figures, slightly expande