arXiv subjects

Marcia C. Barbosa

Publications and source records attributed to Marcia C. Barbosa.

At least 73 records · Page 4Linked to original sources

arXiv2007

Diffusion Anomaly in a three dimensional lattice gas

We investigate the relation between thermodynamic and dynamic properties of an associating lattice gas (ALG) model. The ALG combines a three dimensional lattice gas with particles interacting through a soft core potential and orientational degrees of freedom. From the competition between the directional attractive forces and the soft core potential results two liquid phases, double criticality and density anomaly. We study the mobility of the molecules in this model by calculating the diffusion constant at a constant temperature, $D$. We show that $D$ has a maximum at a density $ρ_{max}$ and a minimum at a density $ρ_{min}<ρ_{max}$. Between these densities the diffusivity differs from the one expected for normal liquids. We also show that in the pressure-temperature phase-diagram the line of extrema in diffusivity is close to the liquid-liquid critical point and it is partially inside the temperature of maximum density (TMD) line.

cond-mat.soft↗

arXiv2006

Liquid polymorphism and density anomaly in a three-dimensional associating lattice gas

We investigate the phase diagram of a three-dimensional associating gas $(ALG)$ model. This model combines orientational ice-like interactions and ``van der Waals'' that might be repulsive, representing, in this case, a penalty for distortion of hydrogen bonds. These interactions can be interpreted as two competing distances making the connection between this model and continuous isotropic soft-core potentials. We present Monte Carlo studies of the $ALG$ model showing the presence of two liquid phase, two critical points and A density anomaly.

cond-mat.soft↗

arXiv2006

Liquid polymorphism, density anomaly and H-bond disruption in an associating lattice gases

We have investigated the effects of either distorting hydrogen bonds or removing proton degeneracy on the thermodynamic properties of a minimal model for associating liquids. The presence of two liquid phases and a density anomaly is unaffected in both cases. Increasing the degeneracy of bonded structures leads to lower temperature critical points and a steeper liquid-liquid coexistence line, implying a low density liquid of larger entropy. Analysis of the hydrogen bond net accross the phase diagram indicates that the density anomaly is accompanied by a steep reduction of hydrogen bond density, which introduces a restriction on a correlation which has been preconized long ago. This feature is present independent of bond distortion or of the presence of proton entropy.

cond-mat.soft↗

arXiv2006

Diffusion Anomaly in an Associating Lattice Gas Model

We investigate the relation between thermodynamic and dynamic properties of an associating lattice gas (ALG) model. The ALG combines a two dimensional lattice gas with particles interacting through a soft core potential and orientational degrees of freedom. From the competition between the directional attractive forces and the soft core potential results two liquid phases, double criticality and density anomaly. We study the mobility of the molecules in this model by calculating the diffusion constant at a constant temperature, $D$. We show that $D$ has a maximum at a density $ρ_{max}$ and a minimum at a density $ρ_{min}<ρ_{max}$. Between these densities the diffusivity differs from the one expected for normal liquids. We also show that in the pressure-temperature phase-diagram the line of extrema in diffusivity is close to the liquid-liquid critical point and it is inside the temperature of maximum density (TMD) line.

cond-mat.stat-mech↗

arXiv2006

Structural anomalies for a three dimensional isotropic core-softened potential

Using molecular dynamics simulations we investigate the structure of a system of particles interacting through a continuous core-softened interparticle potential. We found for the translational order parameter, t, a local maximum at a density $ρ_{t-max}$ and a local minimum at $ρ_{t-min} > ρ_{t-max}$. Between $ρ_{t-max}$ and $ρ_{t-min}$, the $t$ parameter anomalously decreases upon pressure. For the orientational order parameter, $Q_6$, was observed a maximum at a density $ρ_{t-max}< ρ_{Qmax} < ρ_{t-min}$. For densities between $ρ_{Qmax}$ and $ρ_{t-min}$, both the translational (t) and orientational ($Q_6$) order parameters have anomalous behavior. We know that this system also exhibits density and diffusion anomaly. We found that the region in the pressure-temperature phase-diagram of the structural anomaly englobes the region of the diffusion anomaly that is larger than the region limited by the temperature of maximum density. This cascade of anomalies (structural, dynamic and thermodynamic) for our model has the same hierarchy of that one observed for the SPC/E water.

cond-mat.soft↗

arXiv2006

Thermodynamic and Dynamic Anomalies for Dumbbell Molecules Interacting with a Repulsive Ramp-Like Potential

Using collision driven discrete molecular dynamics (DMD), we investigate the thermodynamics and dynamics of systems of 500 dumbbell molecules interacting by a purely repulsive ramp-like discretized potential, consisting of $n$ steps of equal size. We compare the behavior of the two systems, with $n = 18$ and $n = 144$ steps. Each system exhibits both thermodynamic and dynamic anomalies, a density maximum and the translational and rotational mobilities show anomalous behavior. Starting with very dense systems and decreasing the density, both mobilities first increase, reache a maximum, then decrease, reache a minimum, and finally increase; this behavior is similar to the behavior of SPC/E water. The regions in the pressure-temperature plane of translational and rotational mobility anomalies depend strongly on $n$. The product of the translational diffusion coefficient and the orientational correlation time increases with temperature, in contrast with the behavior of most liquids.

cond-mat.soft↗

arXiv2005

Thermodynamic and dynamic anomalies for a three dimensional isotropic core-softened potential

Using molecular dynamics simulations and integral equations (Rogers-Young, Percus-Yevick and hypernetted chain closures) we investigate the thermodynamic of particles interacting with continuous core-softened intermolecular potential. Dynamic properties are also analyzed by the simulations. We show that, for a chosen shape of the potential, the density, at constant pressure, has a maximum for a certain temperature. The line of temperatures of maximum density (TMD) was determined in the pressure-temperature phase diagram. Similarly the diffusion constant at a constant temperature, $D$, has a maximum at a density $ρ_{max}$ and a minimum at a density $ρ_{min}<ρ_{max}$. In the pressure-temperature phase-diagram the line of extrema in diffusivity is outside of TMD line. Although in this interparticle potential lacks directionality, this is the same behavior observed in SPC/E water.

cond-mat.soft↗

arXiv2005

Charge reversal of colloidal particles

A theory is presented for the effective charge of colloidal particles in suspensions containing multivalent counterions. It is shown that if colloids are sufficiently strongly charged, the number of condensed multivalent counterion can exceed the bare colloidal charge leading to charge reversal. Charge renormalization in suspensions with multivalent counterions depends on a subtle interplay between the solvation energies of the multivalent counterions in the bulk and near the colloidal surface. We find that the effective charge is {\it not} a monotonically decreasing function of the multivalent salt concentration. Furthermore, contrary to the previous theories, it is found that except at very low concentrations, monovalent salt hinders the charge reversal. This conclusion is in agreement with the recent experiments and simulations.

cond-mat.soft↗

arXiv2005

Liquid Polymorphism and Double Criticality in a Lattice Gas Model

We analyze the possible phase diagrams of a simple model for an associating liquid proposed previously. Our two-dimensional lattice model combines oreintati onal ice-like interactions and \"{}Van der Waals\"{} interactions which may be repulsive, and in this case represent a penalty for distortion of hydrogen bonds in the presence of extra molecules. These interactions can be interpreted in terms of two competing distances, but not necessarily soft-core. We present mean -field calculations and an exhaustive simulation study for different parameters which represent relative strength of the bonding interaction to the energy penalty for its distortion. As this ratio decreases, a smooth disappearance of the doubl e criticality occurs. Possible connections to liquid-liquid transitions of molecul ar liquids are suggested.

cond-mat.soft↗

arXiv2004

Density Anomaly in Core-Softened Lattice Gas

A two dimensional lattice gas model with ''core-softened'' potential is investigated. Two liquid phases and density anomaly are found. The demixing phase transition between the two liquid phases end at a tricritical point that is also the terminus of a critical line. The density anomaly is related to this continuous line.

cond-mat.stat-mech↗

arXiv2004

Density anomaly in a competing interactions lattice gas model

We study a very simple model of a short-range attraction and an outer shell repulsion as a test system for demixing phase transition and density anomaly. The phase-diagram is obtained by applying mean field analysis and Monte Carlo simulations to a two dimensional lattice gas with nearest-neighbors attraction and next-nearest-neighbors repulsion (the outer shell). Two liquid phases and density anomaly are found. The coexistence line between these two liquid phases meets a critical line between the fluid and the low density liquid at a tricritical point. The line of maximum density emerges in the vicinity of the tricritical point, close to the demixing transition.

cond-mat.stat-mech↗

arXiv2004

Flexible Polyelectrolytes with Monovalent Salt

We present a model for describing flexible polyelectrolytes in a good solvent a nd in the presence of monovalent salt . The molecule composed by $N$ monomers is characterized by the end to end distanc e $R_e=b (Z-1)^γ$ and the number of associated counterions $n$. At high tem peratures the polyelectrolyte behaves as a neutral polymer ($γ=0.588$). Dec reasing the temperature, the macromolecule changes from this extended configurat ion($γ=0.588$) to a stretched form ($γ\approx 1$). At even lower temp eratures, above the Manning condensation threshold, the polyelectrolyte collapse s ($γ\approx 0.3$). Our results show good agreement with simulations.

cond-mat.stat-mech↗

arXiv2003

Complexation in Polyelectrolyte Solution with Divalent Surfactant

We study a simple model of DNA divalent cationic surfactant complexation. We find that the combination of electrostatic and hydrophobic effects leads to a cooperative phenomenon in which as the amphiphile is added to the solution containing DNA, a large fraction of the DNA's charge is neutralized by the condensed divalent cationic surfactants, forming the surfoplex. This binding transition occurs for concentrations that are lower for divalent than for monovalent surfactants. Since the electrostatic strength is larger in the first case and the amount of surfactant lower, we suggest that multivalent amphiphilic molecules would be more efficient than monovalent for transfection.

cond-mat.soft↗

arXiv2003

Dynamic Anomalies of Fluids with Isotropic Doubled-Ranged Potential

Using molecular dynamics simulations we investigate the ability of an analytical three-dimensional double well in reproducing static and dynamic anomalies found experimentally in liquid water. We find anomalous behavior in the stable region of the phase diagram if the outer minimum is deeper than the inner minimum. In the case of a deeper inner minimum, anomalous behavior is also present but inside the unstable region.

cond-mat↗

arXiv2003

Screening of Spherical Colloids beyond Mean Field -- A Local Density Functional Approach

We study the counterion distribution around a spherical macroion and its osmotic pressure in the framework of the recently developed Debye-H"uckel-Hole-Cavity (DHHC) theory. This is a local density functional approach which incorporates correlations into Poisson-Boltzmann theory by adding a free energy correction based on the One Component Plasma. We compare the predictions for ion distribution and osmotic pressure obtained by the full theory and by its zero temperature limit with Monte Carlo simulations. They agree excellently for weakly developed correlations and give the correct trend for stronger ones. In all investigated cases the DHHC theory and its computationally simpler zero temperature limit yield better results than the Poisson-Boltzmann theory.

cond-mat.soft↗

arXiv2001

Criticality in confined ionic fluids

A theory of a confined two dimensional electrolyte is presented. The positive and negative ions, interacting by a $1/r$ potential, are constrained to move on an interface separating two solvents with dielectric constants $ε_1$ and $ε_2$. It is shown that the Debye-Hückel type of theory predicts that the this 2d Coulomb fluid should undergo a phase separation into a coexisting liquid (high density) and gas (low density) phases. We argue, however, that the formation of polymer-like chains of alternating positive and negative ions can prevent this phase transition from taking place.

cond-mat.stat-mech↗

arXiv2001

The Isothermal Binodal Curves Near a Critical Endpoint

Thermodynamics in the vicinity of a critical endpoint with nonclassical exponents $α$, $β$, $γ$, $δ$, $...$ is analyzed in terms of density variables (mole fractions, magnetizations, etc.). The shapes of the isothermal binodals or two-phase coexistence curves are found at andnear the endpoint for symmetric and nonsymmetric situations. The spectator- (or noncritical)-phase binodal at $T=T_{e}$ is characterized by an exponent $(δ+1)/δ$ $(\simeq 1.21)$ with leading corrections of relative order $1/δ$ $(\simeq 0.21)$, $θ_{4}/βδ$ $(\simeq 0.34)$ and $1 -(βδ)^{-1}$$(\simeq 0.36)$; in contrast to classical (van der Waals, mean field, $...$) theory, the critical endpoint binodal is singular with leading exponent $(1-α)/β$ $(\simeq 2.73)$ and corrections which are elucidated; the remaining, $λ$-line binodals also display the `renormalized exponent,' $(1-α)/β$ butwith more singular corrections. (The numerical values quoted here pertain to $(d=3)$-dimensional-fluid or Ising-type systems.)

cond-mat↗

arXiv2001

Static and Dynamic Properties of Stretched Water

We present the results of molecular dynamics simulations of the extended simple point charge (SPC/E) model of water to investigate thethermodynamic and dynamic properties of stretched and supercooled water. We locate the liquid-gas spinodal, and confirm that the spinodal pressure increases monotonically with $T$, supporting thermodynamic scenarios for the phase behavior of supercooled water involving a ``non-reentrant'' spinodal. The dynamics at negative pressure show a minimum in the diffusion constant $D$ when the density is decreased at constant temperature, complementary to the known maximum of $D$ at higher pressures. We locate the loci of minima of $D$ relative to the spinodal, showing that the locus is inside the thermodynamicaly metastable regions of the phase-diagram. These dynamical results reflect the initial enhancement and subsequent breakdown of the tetrahedral structure and of the hydrogen bond network as the density decreases.

cond-mat↗