J. López-Lemus

Oscillatory surface tension due to finite-size effects

The simulation results of surface tension at the liquid-vapor interface are presented for fluids interacting with Lennard Jones and square-well potentials. From the simulation of liquids we have reported [M. González-Melchor et al., J. Chem. Phys. 122, 4503 (2005)] that the components of pressure tensor in parallelepiped boxes are not the same when periodic boundary conditions and small transversal areas are used. This fact creates an artificial oscillatory stress anisotropy in the system with even negative values. By doing direct simulations of interfaces we show in this work that surface tension has also an oscillatory decay at small surface areas; this behavior is opposite to the monotonic decay reported previously for the Lennard Jones fluid. It is shown that for small surface areas, the surface tension of the square-well potential artificially takes negative values and even increases with temperature. The calculated surface tension using a direct simulation of interfaces might have two contributions: one from finite-size effects of interfacial areas due to box geometry and another from the interface. Thus, it is difficult to evaluate the true surface tension of an interface when small surface areas are used. Care has to be taken to use the direct simulation method of interfaces to evaluate the predicted surface tension as a function of interfacial area from capillary-wave theory. The oscillations of surface tension decay faster at temperatures close to the critical point. It is also discussed that a surface area does not show any important effect on coexisting densities, making this method reliable to calculate bulk coexisting properties using small systems.

Stress anisotropy induced by periodic boundary conditions.

Finite size effects due to periodic boundary conditions are investigated using computer simulations in the canonical ensemble. We study liquids with densities corresponding to typical liquid coexistence densities, and temperatures between the triple and critical points. The components of the pressure tensor are computed in order to analyze the finite size effects arising from the size and geometry of the simulation box. Two different box geometries are considered: cubic and parallelepiped. As expected the pressure tensor is isotropic in cubic boxes, but it becomes anisotropic for small noncubic boxes. We argue this is the origin of the anomalous behavior observed recently in the computation of the surface tension of liquid-vapor interfaces. Otherwise, we find that the bulk pressure is sensitive to the box geometry when small simulation boxes are considered. These observations are general and independent of the model liquid considered. We report results for liquids interacting through short range forces, square well and Lennard-Jones, and also long range Coulombic interactions. The effect that small surface areas have on the surface tension is discussed, and some preliminary results at the liquid vapor-interface for the square well potential are given.

Effect of flexibility on surface tension and coexisting densities of water.

Molecular dynamics simulations of pure water at the liquid-vapor interface are performed using direct simulation of interfaces in a liquid slab geometry. The effect of intramolecular flexibility on coexisting densities and surface tension is analyzed. The dipole moment profile across the liquid-vapor interface shows different values for the liquid and vapor phases. The flexible model is a polarizable model. This effect is minor for liquid densities and is large for surface tension. The liquid densities increase from 2% at 300 K to 9% at 550 K when the force field is changed from a fully rigid simple point charge extended (SPCE) model to that of a fully flexible model with the same intermolecular interaction parameters. The increases in surface tension at both temperatures are around 11% and 36%, respectively. The calculated properties of the flexible models are closer to the experimental data than those of the rigid SPCE. The effect of the maximum number of reciprocal vectors (h(z) (max)) and the surface area on the calculated properties at 300 K is also analyzed. The coexiting densities are not sensitive to those variables. The surface tension fluctuates with h(z) (max) with an amplitude larger than 10 mN m(-1). The effect of using small interfacial areas is slightly larger than the error in the simulations.

Liquid–vapour equilibrium of n -alkanes using interface simulations

Molecular Dynamics simulations were performed to calculate liquid–vapour coexisting properties of n-alkane chains up to 16 carbon atoms using interface simulations. The lattice sum or Ewald method on the dispersion forces of the Lennard–Jones potential was applied to calculate the full interaction. The liquid and vapour coexisting densities were obtained for two flexible force field models, NERD and TraPPE-UA, where the intermolecular interactions are of the Lennard–Jones type. We have recently shown [P. Orea, J. López-Lemus, and J. Alejandre, J. Chem. Phys. 123, 114702 (2005)] that the liquid–vapour densities for simple fluids do not depend on interfacial area and therefore it is possible to use a small number of molecules in a simulation. We show that the same trend is found on the simulation of these hydrocarbon molecules. The phase diagram of ethane/n-decane binary mixtures is also obtained at 410.95 K for the NERD model. The simulation results from this work were compared with those obtained using methods with interfaces using large cut-off distances and with methods without interfaces for the same potential model. In both comparisons, excellent agreement was found. The results of liquid density from the TraPPE-UA model are in good agreement with experimental data while those from the NERD model are underestimated at low temperatures. Our findings are consistent with results published by other authors for small hydrocarbons.

Surface tension of hydrocarbon chains at the liquid–vapour interface

Molecular dynamics simulations were performed at constant temperature to obtain the surface tension of hydrocarbon chains at the liquid–vapour interface. The Ewald sum was used to calculate the dispersion forces of the Lennard–Jones potential to take into account the full interaction. The NERD and TraPPE_UA flexible force field models were used to simulate molecules from ethane to hexadecane along the coexistence curve. The simulation results for the TraPPE_UA model are in good agreement with experimental data, whereas the NERD model predicts slightly higher values.

The Wolf method applied to the liquid-vapor interface of water

The Wolf method for the calculation of electrostatic interactions is applied in a liquid phase and at the liquid-vapor interface of water and its results are compared with those from the Ewald sums method. Molecular dynamics simulations are performed to calculate the radial distribution functions at room temperature. The interface simulations are used to obtain the coexisting densities and surface tension along the coexistence curve. The water model is a flexible version of the extended simple point charge model. The Wolf method gives good structural results, fair coexistence densities, and poor surface tensions as compared with those obtained using the Ewald sums method.

Performance of rigid water models in the phase transition of clathrates

Molecular dynamic simulations in the NPT ensemble were performed to analyse the structural properties of methane hydrate by using rigid water models of three, four and five sites (SPC/E, TIP4P and TIP5P). An exploratory study was carried out concerning the capabilities of these water models in the near region of the phase transition line (pressure–temperature). This task was achieved by performing simulations at a constant pressure of 20 atm, varying the temperature from 200 to 300 K. The radial distribution function as well as the coordination number for carbon and oxygen sites were obtained for the above-mentioned temperatures: both of them allow us to observe the stable–unstable phase transition of the methane hydrate. As a result, we can mention that the structural properties estimated with the three sites water model show an excellent agreement with the experimental results, specifically around the phase transition line. In addition, the coordination number becomes a useful criterion to demonstrate the dissociation of the clathrates. On the other hand, the potential of mean force between two methane molecules in water is shown in the same vicinity, evidencing the energetic cost to keep the clathrate in a stable thermodynamic state.

Electrodissociation of clathrate-like structures

In the present work, we develop molecular dynamics (MD) simulations in the NPT (isobaric–isothermic) ensemble to analyse the effect of an external electrostatic field over a cubic methane hydrate crystallite. The amplitude of the field is in the range 0.5–3.0 V/nm. For the simulations, we used the SPC/E rigid water model and a single-site model for methane at a temperature of 248 K and a pressure of 20 bar. When the external electrostatic field is applied, the water dipoles are oriented in such a way that the methane molecules can diffuse far away from the water cages, hence the clathrate dissociation takes place. This last phenomenon was observed for intensities above 1.5 V/nm. Taking the final configuration of each run as input, we develop a new set of MD simulations, and we observe that the stable clathrate is not recovered immediately when the external electrostatic field is turned off due to limitations in the simulation time.

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.

Separating the effects of repulsive and attractive forces on the phase diagram, interfacial, and critical properties of simple fluids

Molecular simulations in the canonical and isothermal-isobaric ensembles were performed to study the effect of varying the shape of the intermolecular potential on the phase diagram, critical, and interfacial properties of model fluids. The molecular interactions were modeled by the Approximate Non-Conformal (ANC) theory potentials. Unlike the Lennard-Jones or Morse potentials, the ANC interactions incorporate parameters (called softnesses) that modulate the steepness of the potential in their repulsive and attractive parts independently. This feature allowed us to separate unambiguously the role of each region of the potential on setting the thermophysical properties. In particular, we found positive linear correlation between all critical coordinates and the attractive and repulsive softness, except for the critical density and the attractive softness which are negatively correlated. Moreover, we found that the physical properties related to phase coexistence (such as span of the liquid phase between the critical and triple points, variations in the P-T vaporization curve, interface width, and surface tension) are more sensitive to changes in the attractive softness than to the repulsive one. Understanding the different roles of attractive and repulsive forces on phase coexistence may contribute to developing more accurate models of liquids and their mixtures.