Minerva González-Melchor

Electrostatic interactions in dissipative particle dynamics using the Ewald sums

The electrostatic interactions in dissipative particle dynamics (DPD) simulations are calculated using the standard Ewald [Ann. Phys. 64, 253 (1921)] sum method. Charge distributions on DPD particles are included to prevent artificial ionic pair formation. This proposal is an alternative method to that introduced recently by Groot [J. Chem. Phys. 118, 11265 (2003)] where the electrostatic field was solved locally on a lattice. The Ewald method is applied to study a bulk electrolyte and polyelectrolyte-surfactant solutions. The structure of the fluid is analyzed through the radial distribution function between charged particles. The results are in good agreement with those reported by Groot for the same systems. We also calculated the radius of gyration of a polyelectrolyte in salt solution as a function of solution pH and degree of ionization of the chain. The radius of gyration increases with the net charge of the polymer in agreement with the trend found in static light scattering experiments of polystyrene sulfonate solutions.

Surface tension at the vapor/liquid interface in an attractive hard-core Yukawa fluid

Canonical ensemble molecular dynamics and Monte Carlo simulations have been performed to study the vapor/liquid coexistence in a hard-core fluid with an attractive Yukawa interaction. Coexisting densities and pressure along the vapor/liquid coexistence line for different ranges of attractive interaction have been evaluated and found to agree well with the Gibbs ensemble Monte Carlo data reported in the literature. To obtain surface tension, the normal and tangential components of the pressure tensor have been calculated during simulations by using a hybrid molecular dynamics algorithm (which combines the hard-core and continuous forces) and by using an original numerical algorithm for the hard-core contribution to the virial in Monte Carlo simulations. We found that surface tension is strongly dependent on the range of attractive interaction, i.e., it drops when the attraction becomes short-ranged. The relation of the attractive hard-core Yukawa potential to the spherically-truncated Lennard-Jones potenti...

Interfacial properties of charge asymmetric ionic liquids

We report molecular dynamics simulations of the coexistence and interfacial properties of ionic liquids as a function of cation/anion, (z +:z −) = (2:−1), (4:−1), charge asymmetry. Our results correct previous computations of the coexistence curve of (2:−1) charge asymmetric systems, obtained via the fine-lattice discretisation method. In agreement with previous computations we report a reduction in the critical temperature and an increase in the critical density with charge asymmetry. We have quantified the interphase potential resulting from the charge asymmetry, by analysing the charge density across the liquid–vapour interface. We show that the Debye–Hückel theory predicts reasonably well the magnitude and temperature dependence of the interphase potential for moderate charge asymmetries (2:−1) but it underestimates, by about 50, the electrostatic potential of ionic liquids with high charge asymmetries (4:−1).

Effect of softness of the potential on the stress anisotropy in liquids

We have performed molecular dynamics simulations of dense liquids using nonconformal and Gaussian potential models. We investigate the effect of the softness of the potential on the pressure tensor of liquids and dense fluids when the simulations are carried out using parallelepiped cells. The combination of periodic boundary conditions and small cross sectional areas induces an anisotropy in the diagonal components of the pressure tensor. This anisotropy results in an artificial stress in the system that has to be taken into account in simulations of explicit interfaces, where the artificial stress introduces errors in the computation of the surface tension. At high liquid densities the stress anisotropy exhibits an oscillatory dependence with the cross sectional area of the simulation box. We find that the softness of the potential has a dramatic effect on the amplitude of the oscillations, which can be significantly reduced in soft potentials, such as those used in the modeling of hydrocarbon liquids or polymers.

Interfacial and coexistence properties of soft spheres with a short-range attractive Yukawa fluid: Molecular dynamics simulations

Molecular dynamics simulations have been carried out to obtain the interfacial and coexistence properties of soft-sphere attractive Yukawa (SAY) fluids with short attraction range, κ = 10, 9, 8, 7, 6, and 5. All our simulation results are new. These data are also compared with the recently reported results in the literature of hard-core attractive Yukawa (HAY) fluids. We show that the interfacial and coexistence properties of both potentials are different. For the surveyed systems, here we show that all coexistence curves collapse into a master curve when we rescale with their respective critical points and the surface tension curves form a single master curve when we plot γ* vs. T/T(c).

Liquid-vapor phase diagram and cluster formation of two-dimensional ionic fluids

Direct molecular dynamics simulations on interfaces at constant temperature are performed to obtain the liquid-vapor phase diagram of the two-dimensional soft primitive model, an equimolar mixture of equal size spheres carrying opposite charges. Constant temperature and pressure simulations are also carried out to check consistency with interface simulations results. In addition, an analysis of the cluster formation of mixtures of particles with charge asymmetry in the range 1:1 to 1:36 at low and high densities is performed. The number of free ions, when plotted as a function of the positive ion charge, Z(+), has an oscillatory behavior and is independent of the density. The formation of aggregates is analyzed in terms of the attraction and repulsion between ions.

Liquid–vapour interface varying the softness and range of the interaction potential

Molecular dynamics simulations in a canonical ensemble were carried out for simple fluids. The inter-particles interaction law is described by the Morse function plus a repulsive term. This kind of combination allows to tune the repulsive term of the interaction function by fitting the range of the attractive well and vice versa. As a relevant result, we show that for an inhomogeneous system the particle softness affects the vapour pressure, the surface tension and also the equilibrium densities of a simple fluid. Lower numerical values for these same properties were obtained by using a more repulsive interaction potential. The differences among these same interfacial properties are bigger when the range of the attractive interaction is longer. The surface tension written in terms of the corresponding critical parameters, such as scaled surface tension, was plotted for different softness degrees. And from this comparison, a unique master curve was not found.

Equilibrium structure of the multi-component screened charged hard-sphere fluid

The generalized mean spherical approximation of the structural properties of the binary charge-symmetric fluid of screened charged hard-spheres of the same diameter, i.e., the screened restricted primitive model, is extended to include binary charge-asymmetric and multi-component fluids. Molecular dynamics simulation data are generated to assess the accuracy of the corresponding theoretical predictions.

The line tension of two-dimensional ionic fluids

Pressure tensor components are very useful in the calculation of the tension associated with a liquid-vapor interface. In this work, we present expressions for the pressure tensor components of two-dimensional ionic fluids, modeled at the level of the primitive model. As an application, we carried out molecular dynamics simulations of liquid-vapor interfaces to calculate the line tension of the 1:1 two-dimensional ionic fluid, whose liquid-vapor coexistence curve had already been obtained in a previous work. The pressure tensor components were validated by simulating states of one phase and reproducing the scalar pressure, previously obtained from bulk simulations and reported in the literature. The effects on the line tension and the coexisting densities, originated by the choice of the Ewald parameters, the cutoff radius, and the interfacial length were also evaluated.

Dopamine and Caffeine Encapsulation within Boron Nitride (14,0) Nanotubes: Classical Molecular Dynamics and First Principles Calculations

Classical molecular dynamics (MD) and density functional theory (DFT) calculations are developed to investigate the dopamine and caffeine encapsulation within boron nitride (BN) nanotubes (NT) with (14,0) chirality. Classical MD studies are done at canonical and isobaric-isothermal conditions at 298 K and 1 bar in explicit water. Results reveal that both molecules are attracted by the nanotube; however, only dopamine is able to enter the nanotube, whereas caffeine moves in its vicinity, suggesting that both species can be transported: the first by encapsulation and the second by drag. Findings are analyzed using the dielectric behavior, pair correlation functions, diffusion of the species, and energy contributions. The DFT calculations are performed according to the BLYP approach and applying the atomic base of the divided valence 6-31g(d) orbitals. The geometry optimization uses the minimum-energy criterion, accounting for the total charge neutrality and multiplicity of 1. Adsorption energies in the dopamine encapsulation indicate physisorption, which induces the highly occupied molecular orbital-lower unoccupied molecular orbital gap reduction yielding a semiconductor behavior. The charge redistribution polarizes the BNNT/dopamine and BNNT/caffeine structures. The work function decrease and the chemical potential values suggest the proper transport properties in these systems, which may allow their use in nanobiomedicine.