Non-monotonic density dependence of the diffusion of DNA fragments in low-salt suspensions

The high linear charge density of 20-base-pair oligomers of DNA is shown to lead to a striking non-monotonic dependence of the long-time self-diffusion on the concentration of the DNA in low-salt conditions. This generic non-monotonic behavior results from both the strong coupling between the electrostatic and solvent-mediated hydrodynamic interactions, and from the renormalization of these electrostatic interactions at large separations, and specifically from the dominance of the far-field hydrodynamic interactions caused by the strong repulsion between the DNA fragments.Comment: 4 pages, 2 figures. Physical Review E, accepted on November 24, 200

Nonlinear screening of charged macromolecules

We present several aspects of the screening of charged macromolecules in an electrolyte. After a review of the basic mean field approach, based on the linear Debye-Huckel theory, we consider the case of highly charged macromolecules, where the linear approximation breaks down and the system is described by full nonlinear Poisson-Boltzmann equation. Some analytical results for this nonlinear equation give some interesting insight on physical phenomena like the charge renormalization and the Manning counterion condensation

Non-linear screening of spherical and cylindrical colloids: the case of 1:2 and 2:1 electrolytes

From a multiple scale analysis, we find an analytic solution of spherical and cylindrical Poisson-Boltzmann theory for both a 1:2 (monovalent co-ions, divalent counter-ions) and a 2:1 (reversed situation) electrolyte. Our approach consists in an expansion in powers of rescaled curvature $1/(\kappa a)$, where $a$ is the colloidal radius and $1/\kappa$ the Debye length of the electrolytic solution. A systematic comparison with the full numerical solution of the problem shows that for cylinders and spheres, our results are accurate as soon as $\kappa a>1$. We also report an unusual overshooting effect where the colloidal effective charge is larger than the bare one.Comment: 9 pages, 11 figure

Pattern formation in binary fluid mixtures induced by short-range competing interactions

Molecular dynamics simulations and integral equation calculations of a simple equimolar mixture of diatomic molecules and monomers interacting via attractive and repulsive short-range potentials show the existence of pattern formation (microheterogeneity), mostly due to depletion forces away from the demixing region. Effective site-site potentials extracted from the pair correlation functions using an inverse Monte Carlo approach and an integral equation inversion procedure exhibit the features characteristic of a short-range attractive and long-range repulsive potential. When charges are incorporated into the model, this becomes a coarse grained representation of a room temperature ionic liquid, and as expected, intermediate range order becomes more pronounced and stable

Casimir-Polder interatomic potential between two atoms at finite temperature and in the presence of boundary conditions

We evaluate the Casimir-Polder potential between two atoms in the presence of an infinite perfectly conducting plate and at nonzero temperature. In order to calculate the potential, we use a method based on equal-time spatial correlations of the electric field, already used to evaluate the effect of boundary conditions on interatomic potentials. This method gives also a transparent physical picture of the role of a finite temperature and boundary conditions on the Casimir-Polder potential. We obtain an analytical expression of the potential both in the near and far zones, and consider several limiting cases of interest, according to the values of the parameters involved, such as atom-atom distance, atoms-wall distance and temperature.Comment: 11 page

Fcc-bcc transition for Yukawa interactions determined by applied strain deformation

Calculations of the work required to transform between bcc and fcc phases yield a high-precision bcc-fcc transition line for monodisperse point Yukawa (screened-Couloumb) systems. Our results agree qualitatively but not quantitatively with previously published simulations and phenomenological criteria for the bcc-fcc transition. In particular, the bcc-fcc-fluid triple point lies at a higher inverse screening length than previously reported.Comment: RevTex4, 9 pages, 6 figures. Discussion of phase coexistence extended, a few other minor clarifications added, referencing improved. Accepted for publication by Physical Review

Mixtures of Charged Colloid and Neutral Polymer: Influence of Electrostatic Interactions on Demixing and Interfacial Tension

The equilibrium phase behavior of a binary mixture of charged colloids and neutral, non-adsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with non-additive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter -- the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion concentration ratios, a free-volume approximation for the free energy is used to compute the fluid phase diagram, which describes demixing into colloid-rich (liquid) and colloid-poor (vapor) phases. Increasing the range of electrostatic interactions shifts the demixing binodal toward higher polymer concentration, stabilizing the mixture. The enhanced stability is attributed to a weakening of polymer depletion-induced attraction between electrostatically repelling macroions. Comparison with predictions of density-functional theory reveals a corresponding increase in the liquid-vapor interfacial tension. The predicted trends in phase stability are consistent with observed behavior of protein-polysaccharide mixtures in food colloids.Comment: 16 pages, 5 figure

Zener double exchange from local valence fluctuations in magnetite

Magnetite (Fe$_{3}$O$_{4}$) is a mixed valent system where electronic conductivity occurs on the B-site (octahedral) iron sublattice of the spinel structure. Below $T_{V}=122$ K, a metal-insulator transition occurs which is argued to arise from the charge ordering of 2+ and 3+ iron valences on the B-sites (Verwey transition). Inelastic neutron scattering measurements show that optical spin waves propagating on the B-site sublattice ($\sim$80 meV) are shifted upwards in energy above $T_{V}$ due to the occurrence of B-B ferromagnetic double exchange in the mixed valent metallic phase. The double exchange interaction affects only spin waves of $\Delta_{5}$ symmetry, not all modes, indicating that valence fluctuations are slow and the double exchange is constrained by electron correlations above $T_{V}$.Comment: 4 pages, 5 figure

Anomalous interactions in confined charge-stabilized colloid

Charge-stabilized colloidal spheres dispersed in weak 1:1 electrolytes are supposed to repel each other. Consequently, experimental evidence for anomalous long-ranged like-charged attractions induced by geometric confinement inspired a burst of activity. This has largely subsided because of nagging doubts regarding the experiments' reliability and interpretation. We describe a new class of thermodynamically self-consistent colloidal interaction measurements that confirm the appearance of pairwise attractions among colloidal spheres confined by one or two bounding walls. In addition to supporting previous claims for this as-yet unexplained effect, these measurements also cast new light on its mechanism.Comment: 8 pages, 5 figures, RevTeX4. Conference proceedings for CODEF-04, Colloidal Dispersions in External Fields, March 29 - April 1, 200

Discrete solvent effects on the effective interaction between charged colloids

Using computer simulations of two charged colloidal spheres with their counterions in a hard sphere solvent, we show that the granular nature of the solvent significantly influences the effective colloidal interaction. For divalent counterions, the total effective force can become attractive generated by counterion hydration, while for monovalent counterions the forces are repulsive and well-described by a solvent-induced colloidal charge renormalization. Both effects are not contained in the traditional "primitive" approaches but can be accounted for in a solvent-averaged primitive model.Comment: 4 pages, 3 figure