Virial expansion for charged colloids and electrolytes

Using a field-theoretic approach, we derive the first few coefficients of the exact low-density (``virial'') expansion of a binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). Our calculations are nonperturbative with respect to the diameters $d_+$ and $d_-$ and charge valences $q_+$ and $q_-$ of positive and negative ions. Consequently, our closed-form expressions for the coefficients of the free energy and activity can be used to treat dilute salt solutions, where typically $d_+ \sim d_-$ and $q_+ \sim q_-$, as well as colloidal suspensions, where the difference in size and valence between macroions and counterions can be very large. We show how to map the TCPHC on a one-component hard-core plasma (OCPHC) in the colloidal limit of large size and valence ratio, in which case the counterions effectively form a neutralizing background. A sizable discrepancy with the standard OCPHC with uniform, rigid background is detected, which can be traced back to the fact that the counterions cannot penetrate the colloids. For the case of electrolyte solutions, we show how to obtain the cationic and anionic radii as independent parameters from experimental data for the activity coefficient.Comment: 15 page

Phase behavior of three-component ionic fluids

We study the phase behavior of solutions consisting of positive and negative ions of valence z to which a third ionic species of valence Z>z is added. Using a discretized Debye-Hueckel theory, we analyze the phase behavior of such systems for different values of the ratio Z/z. We find, for Z/z>1.934, a three-phase coexistence region and, for Z/z>2, a closed (reentrant) coexistence loop at high temperatures. We characterize the behavior of these ternary ionic mixtures as function of charge asymmetry and temperature, and show the complete phase diagrams for the experimentally relevant cases of Z/z=2 and Z/z=3, corresponding to addition of divalent and trivalent ions to monovalent ionic fluids, respectively.Comment: 6 pages, 4 figures; to appear in the European Physical Journal

Electrostatic Interactions in Strongly-Coupled Soft Matter

Charged soft-matter systems--such as colloidal dispersions and charged polymers--are dominated by attractive forces between constituent like-charged particles when neutralizing counterions of high charge valency are introduced. Such counter-intuitive effects indicate strong electrostatic coupling between like-charged particles, which essentially results from electrostatic correlations among counterions residing near particle surfaces. In this paper, the attraction mechanism and the structure of counterionic correlations are discussed in the limit of strong coupling based on recent numerical and analytical investigations and for various geometries (planar, spherical and cylindrical) of charged objects.Comment: 26 pages, 13 figure

Strong-Coupling Theory for Counter-Ion Distributions

The Poisson-Boltzmann approach gives asymptotically exact counter-ion density profiles around charged objects in the weak-coupling limit of low valency and high temperature. In this paper we derive, using field-theoretic methods, a theory which becomes exact in the opposite limit of strong coupling. Formally, it corresponds to a standard virial expansion. Long-range divergences, which render the virial expansion intractable for homogeneous bulk systems, are shown to be renormalizable for the case of inhomogeneous distribution functions by a systematic expansion in inverse powers of the coupling parameter. For a planar charged wall, our analytical results compare quantitatively with extensive Monte-Carlo simulations.Comment: 7 pages, 3 figures; to appear in Europhys. Let

Counterions at Charged Cylinders: Criticality and universality beyond mean-field

The counterion-condensation transition at charged cylinders is studied using Monte-Carlo simulation methods. Employing logarithmically rescaled radial coordinates, large system sizes are tractable and the critical behavior is determined by a combined finite-size and finite-ion-number analysis. Critical counterion localization exponents are introduced and found to be in accord with mean-field theory both in 2 and 3 dimensions. In 3D the heat capacity shows a universal jump at the transition, while in 2D, it consists of discrete peaks where single counterions successively condense.Comment: 4 pages, 3 figures; submitted to Phys. Rev. Lett. (2005

Non-Markovian data-driven modeling of single-cell motility

Trajectories of human breast cancer cells moving on one-dimensional circular tracks are modeled by thenon-Markovian version of the Langevin equation that includes an arbitrary memory function. When averagedover cells, the velocity distribution exhibits spurious non-Gaussian behavior, while single cells are characterizedby Gaussian velocity distributions. Accordingly, the data are described by a linear memory model whichincludes different random walk models that were previously used to account for various aspects of cell motilitysuch as migratory persistence, non-Markovian effects, colored noise, and anomalous diffusion. The memoryfunction is extracted from the trajectory data without restrictions or assumptions, thus making our approachtruly data driven, and is used for unbiased single-cell comparison. The cell memory displays time-delayedsingle-exponential negative friction, which clearly distinguishes cell motion from the simple persistent randomwalk model and suggests a regulatory feedback mechanism that controls cell migration. Based on the extractedmemory function we formulate a generalized exactly solvable cell migration model which indicates thatnegative friction generates cell persistence over long timescales. The nonequilibrium character of cell motionis investigated by mapping the non-Markovian Langevin equation with memory onto a Markovian model thatinvolves a hidden degree of freedom and is equivalent to the underdamped active Ornstein-Uhlenbeck process

Counterion density profiles at charged flexible membranes

Counterion distributions at charged soft membranes are studied using perturbative analytical and simulation methods in both weak coupling (mean-field or Poisson-Boltzmann) and strong coupling limits. The softer the membrane, the more smeared out the counterion density profile becomes and counterions pentrate through the mean-membrane surface location, in agreement with anomalous scattering results. Membrane-charge repulsion leads to a short-scale roughening of the membrane.Comment: 4 pages, 4 figure

Counterions at charge-modulated substrates

We consider counterions in the presence of a single planar surface with a spatially inhomogeneous charge distribution using Monte-Carlo simulations and strong-coupling theory. For high surface charges, multivalent counterions, or pronounced substrate charge modulation the counterions are laterally correlated with the surface charges and their density profile deviates strongly from the limit of a smeared-out substrate charge distribution, in particular exhibiting a much increased laterally averaged density at the surface.Comment: 7 page

New Criticality of 1D Fermions

One-dimensional massive quantum particles (or 1+1-dimensional random walks) with short-ranged multi-particle interactions are studied by exact renormalization group methods. With repulsive pair forces, such particles are known to scale as free fermions. With finite $m$-body forces (m = 3,4,...), a critical instability is found, indicating the transition to a fermionic bound state. These unbinding transitions represent new universality classes of interacting fermions relevant to polymer and membrane systems. Implications for massless fermions, e.g. in the Hubbard model, are also noted. (to appear in Phys. Rev. Lett.)Comment: 10 pages (latex), with 2 figures (not included