Daniel Duque

Interfacial properties of Lennard-Jones chains by direct simulation and density gradient theory

We perform a series of molecular dynamics simulations of Lennard-Jones chains systems, up to tetramers, in order to investigate the influence of temperature and chain length on their phase separation and interfacial properties. Simulation results serve as a test to check the accuracy of a statistical associated fluid theory (soft-SAFT) coupled with the density gradient theory. We focus on surface tension and density profiles. The simulations allow us to discuss the success and limitations of the theory and how to estimate the only adjustable parameter, the influence parameter. This parameter is obtained by fitting the surface tension, and then used to obtain the density profiles in a predictive manner. A good agreement is found if the temperature dependence of this parameter is neglected.(c) 2004 American Institute of Physics.

Some issues on the calculation of interfacial properties by molecular simulation

Some of the pitfalls that may befall molecular simulations of interfaces are discussed. They are all related to the calculation of the pressure tensor profiles, which are needed in order to compute surface tensions. We focus on three controversial points: (1) the calculation of the pressure tensor profiles for polyatomic systems, in particular, when the SHAKE algorithm is employed, (2) the addition of long-range corrections to compensate the truncation of the potential, and (3) the importance of including adequate error intervals with the results. Most of the conclusions are general, but some specifically apply to multiple site molecular-dynamics simulations.

Phase and interface behaviors in type-I and type-V Lennard-Jones mixtures: theory and simulations.

Density gradient theory (DGT) and molecular-dynamics (MD) simulations have been used to predict subcritical phase and interface behaviors in type-I and type-V equal-size Lennard-Jones mixtures. Type-I mixtures exhibit a continuum critical line connecting their pure critical components, which implies that their subcritical phase equilibria are gas liquid. Type-V mixtures are characterized by two critical lines and a heteroazeotropic line. One of the two critical lines begins at the more volatile pure component critical point up to an upper critical end point and the other one comes from the less volatile pure component critical point ending at a lower critical end point. The heteroazeotropic line connects both critical end points and is characterized by gas-liquid-liquid equilibria. Therefore, subcritical states of this type exhibit gas-liquid and gas-liquid-liquid equilibria. In order to obtain a correct characterization of the phase and interface behaviors of these types of mixtures and to directly compare DGT and MD results, the global phase diagram of equal-size Lennard-Jones mixtures has been used to define the molecular parameters of these mixtures. According to our results, DGT and MD are two complementary methodologies able to obtain a complete and simultaneous prediction of phase equilibria and their interfacial properties. For the type of mixtures analyzed here, both approaches have shown excellent agreement in their phase equilibrium and interface properties in the full concentration range.

Molecular theory of hydrophobic mismatch between lipids and peptides

Effects of the mismatch between the hydrophobic length d, of transmembrane alpha helices of integral proteins and the hydrophobic thickness, Dh, of the membranes they span are studied theoretically utilizing a microscopic model of lipids. In particular, we examine the dependence of the period of a lamellar phase on the hydrophobic length and volume fraction of a rigid, integral, peptide. We find that the period decreases when a short peptide, such that d Dh, is inserted. The effect is due to the replacement of extensible lipid tails by rigid peptide. As the peptide length is increased, the lamellar period continues to increase, but at a slower rate, and can eventually decrease. The amount of peptide which fails to incorporate and span the membrane increases with the magnitude of the hydrophobic mismatch |d−Dh|. We explicate these behaviors which are all in accord with experiment. Predictions are made for t...

Theory of T junctions and symmetric tilt grain boundaries in pure and mixed polymer systems

We apply self-consistent-field theory to T junctions and symmetric tilt grain boundaries in block copolymer systems with and without the addition of homopolymer. We find that, in the absence of homopolymer, T junctions have a larger free energy per unit area than that of the symmetric tilt junctions with which they compete except for a range of angles between about 100° and 130°. With the addition of homopolymer, this range increases. These results are quite consistent with experiment. As the angle between grains increases towards 180°, the T junction undergoes a morphological change somewhat similar to that which occurs in symmetric tilt grain boundaries. At the onset of this change, the free energy per unit area decreases markedly.

Sulfur hexafluoride's liquid-vapor coexistence curve, interfacial properties, and diffusion coefficients as predicted by a simple rigid model.

We present here molecular-dynamics simulation results of the vapor-liquid coexistence curve, surface tension, and self-diffusion coefficients of sulfur hexafluoride. Sulfur hexafluoride is modeled as a rigid molecule, following the model proposed by Pawley [Mol. Phys. 43, 1321 (1981)]. Vapor-liquid coexistence curve and surface tension are obtained through direct molecular-dynamic simulations in the NVT ensemble. Simulation results are able to reproduce the qualitative shape of the vapor-liquid envelope. However, lower densities, a higher critical temperature, and an overestimated surface tension are obtained here. Those deviations are explained on the basis of the rigidity of the molecular model used. Self-diffusion coefficients are calculated from simulations in the NVE ensemble for different gas states at atmospheric pressure. The rigid model performs better for dynamical properties since simulation results provide very good agreement with available experimental data in this case.

Analysis of electron interactions in dielectric gases

We present and discuss results concerning electron interactions processes of dielectric gases and their relationship with the macroscopic behavior of these gases, in particular, with their dielectric strength. Such analysis is based on calculating energies of reactions for molecular ionization, dissociative ionization, parent negative ion formation, and dissociative electron attachment processes. We hypothesize that the estimation of the required energy for a reduced number of processes that take place in electrically stressed gases could be related to the gas’ capability to manage the electron flow during an electrical discharge. All calculations were done with semiempirical quantum chemistry methods, including an initial optimization of molecular geometry and heat of formation of the dielectric gases and all of species that appear during electron interaction reactions. The performance of semiempirical methods Austin model 1 and Parametric model 3 (PM3) was compared for several compounds, PM3 being super...

Calculation of the force between surfaces coated with grafted molecules by molecular simulation

We discuss the calculation of the force between surfaces coated with anchored molecules. This force is related to the pressure and can therefore be calculated by the usual means: either by summing over all surface-particle forces or from the virial. However, we argue that the grafting of the molecule must be included by means of a restraining potential-otherwise, nonphysical results can be obtained, such as the appearance of a net force even when the particles are spaced very far away. Bond-stretching potentials are also required if the virial is employed.

A molecular-based equation of state for process engineering

Abstract We outline here some of the steps we are taking towards the development of reliable tools for quantitative predictions of thermodynamic properties of complex fluids with equations based on statistical mechanics. The long term objective is to provide a user-friendly computer code and a wide database of molecular parameters for different compounds, able to be implemented in a process simulator. We have observed that the keys of the success when using molecular modelling tools for predictions rely on the selection of the appropriate model, representative of the molecular structure, and the use of physically meaningful molecular parameters.

Comment on "Spin-1 aggregation model in one dimension".

Girardi and Figueiredo have proposed a simple model of aggregation in one dimension to mimic the self assembly of amphiphiles in aqueous solution [Phys. Rev. E 62, 8344 (2000)]. We point out that interesting results can be obtained if a different set of interactions is considered, instead of their choice (the s=1 Ising model).