Teena Goel

Excess entropy scaling of transport properties of Lennard-Jones chains

Excess-entropy scaling relationships for diffusivity and viscosity of Lennard-Jones chain fluids are tested using molecular dynamics simulations for chain sizes that are sufficiently small that chain entanglement effects are insignificant. The thermodynamic excess entropy S(e) is estimated using self-associating fluid theory (SAFT). A structural measure of the entropy S(2) is also computed from the monomer-monomer pair correlation function, g(m)(r). The thermodynamic and structural estimators for the excess entropy are shown to be very strongly correlated. The dimensionless center-of-mass diffusivities, D(cm) (*), obtained by dividing the diffusivities by suitable macroscopic reduction parameters, are shown to conform to the excess entropy scaling relationship, D(cm) (*)=A(n) exp(alpha(n)S(e)), where the scaling parameters depend on the chain length n. The exponential parameter alpha(n) varies as -(1n) while A(n) varies approximately as n(-0.5). The scaled viscosities obey a similar relationship with scaling parameters B(n) and beta(n) where beta(n) varies as 1n and B(n) shows an approximate n(0.6) dependence. In accordance with the Stokes-Einstein law, for a given chain length, alpha(n)=-beta(n) within statistical error. The excess entropy scaling parameters associated with the transport properties therefore display a simple dependence on chain length.

Structure of spherical electric double layers: A density functional approach

A density functional theory is presented for the structure of spherical electric double layers within the restricted primitive model, where the macroion is considered as a hard sphere having uniform surface charge density, the small ions as charged hard spheres, and the solvent is taken as a dielectric continuum. The theory is partially perturbative as the hard-sphere contribution to the one-particle correlation function is evaluated using suitably averaged weighted density and the ionic part is obtained through a second-order functional Taylor expansion around the uniform fluid. The theory is in quantitative agreement with Monte Carlo simulation for the density profiles and the zeta potentials over a wide range of macroion sizes and electrolyte concentrations. The theory is able to provide interesting insights about the layering and the charge inversion phenomena occurring at the interface.

Molecular solvent model of cylindrical electric double layers: A systematic study by Monte Carlo simulations and density functional theory

We present the Monte Carlo simulation and density functional study of structure of cylindrical double layers considering solvent as the third component. We have chosen molecular solvent model, where ions and solvent molecules are considered as charged and neutral hard spheres, respectively, having equal diameter. The polyionic cylinder is modeled as an infinite, rigid, and impenetrable charged hard cylinder surrounded by the electrolyte and the solvent spheres. The theory is partially perturbative where the hard-sphere interactions are treated within the weighted density approach, the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The Monte Carlo simulations have been performed in canonical ensemble. The system is studied at varying concentrations of electrolyte ions and the solvent molecules, at different valences of the electrolyte, at different sizes of hard spheres, and at varying surface charge density. The theory and the simulation results are found to be in good agreement at different parametric conditions. The hard-sphere exclusion effects due to molecular nature of the solvent are shown to have special implications in characterizing diffuse layer phenomena such as layering and charge inversion.

Structure of cylindrical electric double layers : A systematic study by Monte Carlo simulations and density functional theory

We present a systematic study of the structure of cylindrical double layers to envisage the distribution of small ions around a cylindrical polyion through canonical Monte Carlo simulation and density functional theory. The polyion is modeled as an infinite, rigid, and impenetrable charged cylinder surrounded by charged hard spheres of equal diameter modeled for small ions of the electrolyte. The solvent is considered as dielectric continuum. The theory is partially perturbative where the hard sphere contribution to the total excess free energy is evaluated using weighted density approximation, and the ionic interactions are calculated using quadratic Taylor expansion with respect to a uniform fluid. The system is studied over a wide range of parameters, viz., ionic concentrations, valences, and ionic sizes as well as for varying axial charge densities of the polyion. The theoretical predictions are observed to be in good agreement with that of simulation results. Some interesting phenomena relating to the width of the diffuse layer, mean electrostatic potential, and charge inversion have been observed to be dependent on different parametric conditions.

Structure of short polymers at interfaces: a combined simulation and theoretical study.

The structure of polymers confined between surfaces is studied using computer simulation and a density functional approach. The simple model system considers the polymer molecule as a pearl necklace of freely jointed hard spheres, having attractions among the beads, confined between attractive surfaces. This approach uses the universality of the free-energy functional to obtain the self-consistent field required in the single chain simulation. The second-order direct correlation function for the uniform bulk fluid required as input has been calculated from the reference interaction site model integral equation theory using mean spherical approximation. The theoretical results are shown to compare well with the Monte Carlo simulation results for varying densities, chain lengths, and with different attractive interaction parameters. The simulation results on the conformational properties give important indications regarding the behavior of chains as they approach the surfaces.

Three component model of cylindrical electric double layers containing mixed electrolytes: A systematic study by Monte Carlo simulations and density functional theory

The structure of electric double layer around a hard rigid impenetrable cylindrical polyion is studied using density functional theory as well as Monte Carlo simulations. The three component model, presented here, is an extension of solvent primitive model where the solvent molecules are treated as the neutral hard spheres, counterions and coions as the charged hard spheres, all of equal diameters, and in addition the mixture of mono- and multivalent counterions are also considered. The theory is partially perturbative where the hard sphere interactions are treated within the weighted density approach and the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The theoretical predictions in terms of the density profiles and the mean electrostatic potential profiles are found to be in good agreement with the simulation results. The presence of neutral hard spheres incorporate the effects of exclude volume interactions (ionic size correlations) while the mixture of mono- and multivalent counterions enhance the ionic charge correlation effects. Thus, this model study shows clear manipulations of ionic size and charge correlations in dictating the ionic density profiles as well as mean electrostatic potential profiles of the diffuse layer. The behavior of diffused double layer has been characterized at varying ionic concentrations, at different concentration ratios of mono- and multivalent counterions of mixed electrolytes, at different diameters of hard spheres, and at varying polyion surface charge density.

Effect of ionic size on the structure of cylindrical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

The effect of ionic size on the diffuse layer characteristics of a cylindrical electric double layer is studied using density functional theory and Monte Carlo simulations for the restricted primitive model and solvent primitive model. The double layer is comprised of an infinitely long, rigid, impenetrable charged cylinder also referred to as the polyion, located at the center of a cylindrical cell containing the electrolyte, which is composed of charged hard spheres and the solvent molecules as neutral hard spheres (in the case of the solvent primitive model). The diameters of all the hard spheres are taken to be the same. The theory is based on a partially perturbative scheme, where perturbation is used to approximate the ionic interactions and the hard sphere contribution is treated within the weighted density approach. The Monte Carlo simulations are performed in the canonical ensemble. The zeta potential profiles as a function of the polyion surface charge density are presented for cylindrical double layers at different ionic concentrations, ionic valences, and different hard sphere (ionic and the solvent) diameters of 2, 3, and 4 Å. The theory agrees quite well with the simulation results for a wide range of system parametric conditions and is capable of showing the maximum and minimum in the zeta potential value for systems having divalent counterions. The steric effects due to the presence of solvent molecules play a major role in characterizing the zeta potential and the ionic density profiles. A noticeable change in the concavity of the zeta potential plots with increasing particle size at very low concentrations of monovalent electrolytes is suggestive of the occurrence of infinite differential capacitance for such systems.

Fluorescence Dynamics of Double- and Single-Stranded DNA Bound to Histone and Micellar Surfaces

The study of structure and dynamics of bound DNA has special implications in the context of its biological as well as material functions. It is of fundamental importance to understand how a binding surface affects different positions of DNA with respect to its open ends. Because double-stranded (ds) and single-stranded (ss) DNA are the predominant functional forms, we studied the site-specific dynamics of these DNA forms, bound to the oppositely charged surface of histones, and compared the effects with that of DNA bound to cetyltrimethyl ammonium bromide micelles. We utilized a time-resolved fluorescence technique using fluorescent base analogue 2-aminopurine located at specific positions of synthetic poly-A DNA strands to obtain fluorescence lifetime and anisotropy information. It is observed that the binding leads to overall rigidification of the DNA backbone, and the highly flexible ends show drastic dampening of their internal dynamics as well as the fraying motions. In the case of ds-DNA, we find that the binding not only decreases the flexibility but also leads to significant weakening of base-stacking interactions. An important revelation that strong binding between DNA and the binding agents (histones as well as micelles) does not dampen the internal dynamics of the bases completely suggests that the DNA in its bound form stays in some semiactive state, retaining its full biological activity. Considering that the two binding agents (histones and micelles) are chemically very different, an interesting comparison is made between DNA-histones and DNA-micelle interactions.

Effect of attractive interactions on the structure of polymer melts confined between surfaces: A density-functional approach

A density-functional theory is presented to study the structure of polymers, having attractive interactions, confined between attractive surfaces. The theory treats the ideal-gas free-energy functional exactly and uses weighted density approximation for the hard-chain contribution to the excess free-energy functional. The bulk interactions of freely jointed hard spheres are obtained from generalized Flory equation of state and the attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions are found to be in quite good agreement with the Monte Carlo simulation results for varying densities, chain lengths, and different interaction potentials. The results confirm important implications of using different approximations for the hard-sphere and attractive interactions.

A self-consistent density-functional approach to the structure of electric double layer: charge-asymmetric electrolytes

A self-consistent density-functional approach has been employed to study the structure of an electric double layer formed from a charge-asymmetric (2:l) electrolyte within the restricted primitive model which corresponds to charged hard sphere ions and a continuum solvent. The particle correlation due to hard-core exclusions is evaluated by making use of the universality of the density functionals and the correlation function of the uniform hard sphere fluid obtained through the integral equation theory with an accurate closure relation whereas mean spherical approximation is employed for the electrical contribution. Numerical results on the diffuse layer potential drop, ionic density profile, and the mean electrostatic potential near the electrode surface at several surface charge densities are found to be in quantitative agreement with the available simulation data.