Macroion solutions in the cell model studied by field theory and Monte Carlo simulations

Aqueous solutions of charged spherical macroions with variable dielectric permittivity and their associated counterions are examined within the cell model using a field theory and Monte Carlo simulations. The field theory is based on separation of fields into short- and long-wavelength terms, which are subjected to different statistical-mechanical treatments. The simulations were performed by using a new, accurate, and fast algorithm for numerical evaluation of the electrostatic polarization interaction. The field theory provides counterion distributions outside a macroion in good agreement with the simulation results over the full range from weak to strong electrostatic coupling. A low-dielectric macroion leads to a displacement of the counterions away from the macroion

Electrostatic depletion forces between planar surfaces

The interaction between two dielectric plates immersed in an electrolyte solution is examined by using a variational perturbation approximation for the grand partition function. This approach differs from previous treatments in that the screening length between the plates is treated as a variational parameter. A key finding is that adjacent to each plate is a layer of ion depletion with thickness given by about one-half of a Bjerrum length. Consequently, for plate-plate separations less than the Bjerrum length, nearly all the electrolyte is excluded from between the plates, and the interaction is given by the sum of a van der Waals interaction and an attractive osmotic depletion force. In contrast to the predictions of previous theories, the interaction between the plates at short range increases with increasing electrolyte concentration and may provide an important contribution to the salt-induced attraction, commonly referred to as salting out. Because the range of the osmotic depletion force is roughly equal to the Bjerrum length, it increases with the square of the valency of the electrolyte. At larger plate-plate separations, the van der Waals interaction is screened as electrolyte enters the space between the plates, leading to an exponential decay of the interactions, as has been previously observed. However, this interaction is slightly stronger than that previously predicted, due to ion depletion from the surface of the interface, also this effect increases with increasing electrolyte concentration

A group contribution method for predicting the solubility of mercury

Mercury is a toxic and corrosive element, and understanding its partitioning within ecosystems and industrial processes is of vital importance. The solubility of mercury in normal alkanes, aromatics, water and alcohols is predicted using widely used Soave-Redlich-Kwong equation of state in combination with a group contribution method to estimate binary interaction parameters. The interaction parameters between elemental mercury and seven other molecular groups were determined in this work by fitting available solubility data for mercury. The solubility in the studied solvents was accurately described. This work allows the prediction of the thermodynamic behavior of elemental mercury in a wide variety of solvents, solvent mixtures, and operating conditions where experimental data are unavailabl

The influence of excluded volume and excess ion polarizability on the capacitance of the electric double layer

We apply a modified Poisson-Boltzmann theory which permits ions of different sizes and excess polarizabilities to the study of these properties' effects on the differential capacitance of the electric double layer. For a planar electrode, we find an analytical expression for the differential capacitance, which is examined in the limits of low and high applied potential. In the low potential limit, a reduction of the solution relative permittivity caused by the ion polarizability causes the differential capacitance to decrease above a certain concentration, relative to the Gouy-Chapman-Stern theory. A similar effect is observed for the excluded volume, but only if the ions are of different sizes. In the high potential limit, the differential capacitance decreases inversely with the square root of the applied voltage. In a mixed electrolyte, asymmetries in both ion size and excess polarizability alter the surface adsorption of species: at high potentials, smaller ions displace larger ions and less polarizable ions displace more polarizable ions. The extent of the displacement agrees favorably with experimental data. A further consequence of this displacement is the appearance of a second peak in the differential capacitance, which is enhanced by excess ion polarizability

A field theoretic approach to the electric interfacial layer : mixture of trivalent rod-like and monovalent point-like ions between charged walls

In this paper, we study the interaction between charged macroions (surfaces) immersed in a solution of oppositely charged, rod-like counterions and point-like co-ions. The system is modeled by a field theoretic approach, which was extended to treat mixtures of rod- and point-like ions. The theory is applicable from the weak to the intermediate through to the strong coupling regimes. In the weak coupling limit, the force between the charged surfaces are only repulsive. In the intermediate coupling regime, the rod-like ions can induce attractive force between the charged surfaces. In the strong coupling limit, the inter-ionic charge correlations dominate the attractive forces at short separations between the charged surfaces

On the electrostatics of DNA in chromatin

We examine the interaction between DNA molecules immersed in an aqueous solution of oppositely charged, trivalent spermidine molecules. The DNA molecules are modeled as planar, likecharged surfaces immersed in an aqueous solution of multivalent, rod-like ions consisting of rigidly bonded point charges. An approximate field theory is used to determine the properties of this system from the weak to the intermediate through to the strong coupling regimes. In the weak coupling limit, the interaction between the charged surfaces is only repulsive, whereas in the intermediate coupling regime, the rod-like ions with spatial charge distribution can induce attractive force between the charged surfaces. In the strong coupling limit, the inter-ionic charge correlations induce attractive interaction at short separations between the surfaces. This theoretical study can give new insights in the problem of interaction between DNA molecules mediated by trivalent spermidine molecules

Exact on-event expressions for discrete potential systems

The properties of systems composed of atoms interacting though discrete potentials are dictated by a series of events which occur between pairs of atoms. There are only four basic event types for pairwise discrete potentials and the square-well/shoulder systems studied here exhibit them all. Closed analytical expressions are derived for the on-event kinetic energy distribution functions for an atom, which are distinct from the Maxwell-Boltzmann distribution function. Exact expressions are derived that directly relate the pressure and temperature of equilibrium discrete potential systems to the rates of each type of event. The pressure can be determined from knowledge of only the rate of core and bounce events. The temperature is given by the ratio of the number of bounce events to the number of disassociation/association events. All these expressions are validated with event-driven molecular dynamics simulations and agree with the data within the statistical precision of the simulations

Crystal templating through liquid–liquid phase separation

Controlled induction of crystal nucleation is a highly desirable but elusive goal. Attempts to speed up crystallization, such as high super saturation or working near a liquid–liquid critical point, always led to irregular and uncontrollable crystal growth. Here, we show that under highly nonequilibrium conditions of spinodal decomposition, water crystals grow as thin wires in a template-less formation of “Haareis”. This suggests that such nonequilibrium conditions may be employed more widely as mechanisms for crystal growth control

Interactions between charged surfaces mediated by stiff, multivalent zwitterionic polymers

The interaction between like-charged objects in electrolyte solutions can be heavily altered by the presence of multivalent ions which possess a spatially distributed charge. In this work, we examine the influence of stiff, multivalent zwitterionic polymers on the interaction between charged surfaces using a splitting field theory previously shown to be accurate from the weak to the intermediate through to the strong electrostatic coupling regimes. The theory is compared to Monte Carlo simulations and good agreement is found between both approaches. For surface separations shorter than the polymer length, the polymers are mainly oriented parallel to the surfaces, and the surface-surface interaction is repulsive. When the surface separation is comparable to the length of polymers, the polymers have two main orientations. The first corresponds to the polymers adsorbed to the surface with their centers located near to or in contact with the surface; the second corresponds to polymers which are perpendicular to the charged surfaces, bridging both surfaces and leading to an attractive force between them. Increasing the surface charge density leads to a more pronounced attraction via bridging. At surface separations greater than the polymer length, the polymers in the center of the system are still mainly perpendicular to the surfaces, due to "chaining" between zwitterions that enable them to bridge the surfaces at larger separations. This leads to an attractive interaction between the surfaces with a range significantly longer than the length of the polymers