The one-component plasma: a conceptual approach

The one-component plasma (OCP) represents the simplest statistical mechanical model of a Coulomb system. For this reason, it has been extensively studied over the last forty years. The advent of the integral equations has resulted in a dramatic improvement in our ability to carry out numerical calculations, but came at the expense of a physical insight gained in a simpler analytic theory. In this paper we present an extension of the Debye-Hueckel (DH) theory to the OCP. The theory allows for analytic calculations of all the thermodynamic functions, as well as the structure factor. The theory explicitly satisfies the Stillinger-Lovett and, for small couplings, the compressibility sum rules, implying its internal self consistency.Comment: 28 pages, 5 Postscript figures, uses elsart.sty, accepted for publication in Physica

Density-functional theory for attraction between like-charged plates

We study the interactions between two negatively charged macroscopic surfaces confining positive counterions. A density-functional approach is introduced which, besides the usual mean-field interactions, takes into account the correlations in the positions of counterions. The excess free energy is derived in the framework of the Debye-H{\"u}ckel theory of the one-component plasma, with the homogeneous density replaced by a weighted density. The minimization of the total free energy yields the density profile of the microions. The pressure is calculated and compared with the simulations and the results derived from integral equations theories. We find that the interaction between the two plates becomes attractive when their separation distance is sufficiently small and the surface charge density is larger than a threshold value.Comment: 7 pages, 4 Postscript figures, uses multicol.st

Theory of High-Force DNA Stretching and Overstretching

Single molecule experiments on single- and double stranded DNA have sparked a renewed interest in the force-extension of polymers. The extensible Freely Jointed Chain (FJC) model is frequently invoked to explain the observed behavior of single-stranded DNA. We demonstrate that this model does not satisfactorily describe recent high-force stretching data. We instead propose a model (the Discrete Persistent Chain, or ``DPC'') that borrows features from both the FJC and the Wormlike Chain, and show that it resembles the data more closely. We find that most of the high-force behavior previously attributed to stretch elasticity is really a feature of the corrected entropic elasticity; the true stretch compliance of single-stranded DNA is several times smaller than that found by previous authors. Next we elaborate our model to allow coexistence of two conformational states of DNA, each with its own stretch and bend elastic constants. Our model is computationally simple, and gives an excellent fit through the entire overstretching transition of nicked, double-stranded DNA. The fit gives the first values for the elastic constants of the stretched state. In particular we find the effective bend stiffness for DNA in this state to be about 10 nm*kbt, a value quite different from either B-form or single-stranded DNAComment: 33 pages, 11 figures. High-quality figures available upon reques

Reversible stretching of homopolymers and random heteropolymers

We have analyzed the equilibrium response of chain molecules to stretching. For a homogeneous sequence of monomers, the induced transition from compact globule to extended coil below the $\theta$-temperature is predicted to be sharp. For random sequences, however, the transition may be smoothed by a prevalence of necklace-like structures, in which globular regions and coil regions coexist in a single chain. As we show in the context of a random copolymer, preferential solvation of one monomer type lends stability to such structures. The range of stretching forces over which necklaces are stable is sensitive to chain length as well as sequence statistics.Comment: 14 pages, 4 figure

The field theoretic derivation of the contact value theorem in planar geometries and its modification by the Casimir effect

The contact value theorem for Coulomb gases in planar or film-like geometries is derived using a Hamiltonian field theoretic representation of the system. The case where the film is enclosed by a material of different dielectric constant to that of the film is shown to contain an additional Casimir-like term which is generated by fluctuations of the electric potential about its mean-field value.Comment: Link between Sine-Gordon and Coulomb gas pressures via subtraction of self interaction terms included. Discussion of results within Debye-Huckel approximation included. Added reference

Counterion Condensation and Fluctuation-Induced Attraction

We consider an overall neutral system consisting of two similarly charged plates and their oppositely charged counterions and analyze the electrostatic interaction between the two surfaces beyond the mean-field Poisson-Boltzmann approximation. Our physical picture is based on the fluctuation-driven counterion condensation model, in which a fraction of the counterions is allowed to ``condense'' onto the charged plates. In addition, an expression for the pressure is derived, which includes fluctuation contributions of the whole system. We find that for sufficiently high surface charges, the distance at which the attraction, arising from charge fluctuations, starts to dominate can be large compared to the Gouy-Chapmann length. We also demonstrate that depending on the valency, the system may exhibit a novel first-order binding transition at short distances.Comment: 15 pages, 8 figures, to appear in PR

Anisotropy studies around the galactic centre at EeV energies with the Auger Observatory

Data from the Pierre Auger Observatory are analyzed to search for anisotropies near the direction of the Galactic Centre at EeV energies. The exposure of the surface array in this part of the sky is already significantly larger than that of the fore-runner experiments. Our results do not support previous findings of localized excesses in the AGASA and SUGAR data. We set an upper bound on a point-like flux of cosmic rays arriving from the Galactic Centre which excludes several scenarios predicting sources of EeV neutrons from Sagittarius $A$. Also the events detected simultaneously by the surface and fluorescence detectors (the `hybrid' data set), which have better pointing accuracy but are less numerous than those of the surface array alone, do not show any significant localized excess from this direction.Comment: Matches published versio

Aqueous Suspensions Of Charged Spherical Colloids: Dependence Of The Surface Charge On Ionic Strength, Acidity, And Colloid Concentration

We theoretically investigate the dependence of the surface charge developed on charged spherical colloids upon several environmental parameters: the ionic strength of the monovalent added electrolyte, acidity (stabilized by a pH buffer solution), and colloid concentration. In the framework of the mean-field Poisson-Boltzmann spherical cell model, we include the charged colloid-microion correlations into the buffer equation, and we allow for the specific binding of ions to the ionizable groups on the colloid surface. Theoretical predictions are compared to the results obtained under the planar-symmetry Gouy-Chapman approximation and analyzed for the experimental conditions of an aqueous dispersion of the phospholipid dimyristoyl phosphatidylglycerol (DMPG). Experimental measurements of the partition ratio of an aqueous soluble cationic spin label on buffered dispersions of polyanionic unilamellar vesicles of DMPG in the presence of added monovalent salt are theoretically interpreted in terms of ion partition due to electrostatic interactions. We show that the specific binding of the probe must be admitted to explain the experimental results. © 2005 American Chemical Society.21241100511016Lodish, H., Berk, A., Zipursky, S.L., Matsudaira, P., Baltimore, D., Darnell, J., (2000) Molecular Cell Biology, 4th Ed., , W. H. Freeman: New YorkAlberts, B., Johnson, A., Lewis, J., Raff, M., Roberts, K., Walter, P., (2002) Molecular Biology of the Cell, 4th Ed., , Garland: New YorkHonig, B., Nicholls, A., (1995) Science, 268, p. 1144Israelachvili, J.N., (1992) Intermolecular and Surface Forces, 2nd Ed., , Academic Press: LondonLamy-Freund, M.T., Riske, K.A., (2003) Chem. Phys. 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Phase Transitions And Spatially Ordered Counterion Association In Ionic-lipid Membranes: A Statistical Model

We propose a statistical model to account for the gel-fluid anomalous phase transitions in charged bilayer- or lamellae-forming ionic lipids. The model Hamiltonian comprises effective attractive interactions to describe neutral-lipid membranes as well as the effect of electrostatic repulsions of the discrete ionic charges on the lipid headgroups. The latter can be counterion dissociated (charged) or counterion associated (neutral), while the lipid acyl chains may be in gel (low-temperature or high-lateral-pressure) or fluid (high-temperature or low-lateral-pressure) states. The system is modeled as a lattice gas with two distinct particle types-each one associated, respectively, with the polar-headgroup and the acyl-chain states-which can be mapped onto an Ashkin-Teller model with the inclusion of cubic terms. The model displays a rich thermodynamic behavior in terms of the chemical potential of counterions (related to added salt concentration) and lateral pressure. In particular, we show the existence of semidissociated thermodynamic phases related to the onset of charge order in the system. This type of order stems from spatially ordered counterion association to the lipid headgroups, in which charged and neutral lipids alternate in a checkerboard-like order. Within the mean-field approximation, we predict that the acyl-chain order-disorder transition is discontinuous, with the first-order line ending at a critical point, as in the neutral case. Moreover, the charge order gives rise to continuous transitions, with the associated second-order lines joining the aforementioned first-order line at critical end points. We explore the thermodynamic behavior of some physical quantities, like the specific heat at constant lateral pressure and the degree of ionization, associated with the fraction of charged lipid headgroups. © 2011 American Physical Society.843Nagle, J.F., (1980) Ann. Rev. Phys. 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Phase Transitions And Spatially Ordered Counterion Association In Ionic-lipid Membranes: Theory Versus Experiment

Aqueous dispersions of phosphatidylglycerol (PG) lipids may present an anomalous chain-melting transition at low ionic strengths, as seen by different experimental techniques such as calorimetry or light scattering. The anomaly disappears at high ionic strengths or for longer acyl-chain lengths. In this article, we use a statistical model for the bilayer that distinguishes both lipid chain and headgroup states in order to compare model and experimental thermotropic and electrical properties. The effective van der Waals interactions among hydrophobic chains compete with the electrostatic repulsions between polar headgroups, which may be ionized (counterion dissociated) or electrically neutral (associated with counterions). Electric degrees of freedom introduce new thermotropic charge-ordered phases in which headgroup charges may be spatially ordered, depending on the electrolyte ionic strength, introducing a new rationale for experimental data on PGs. 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