Computer simulation of a gas–liquid surface. Part 1
01 Jan 1977-Journal of the Chemical Society, Faraday Transactions (The Royal Society of Chemistry)-Vol. 73, Iss: 7, pp 1133-1144
TL;DR: In this article, Monte Carlo and molecular dynamic simulations of the surface of a system of Lennard-Jones (12, 6) molecules have been carried out at temperatures which span most of the liquid range, showing that the density profile, as a function of height, falls monotonically from the density of the bulk liquid to that of gas.
Abstract: The gas–liquid surface of a system of Lennard-Jones (12, 6) molecules has been simulated by Monte Carlo and by Molecular Dynamic methods at temperatures which span most of the liquid range. For systems of 255 molecules the two methods lead to similar results and this agreement confirms that the density profile, as a function of height, falls monotonically from the density of the bulk liquid to that of the gas. The thickness of the surface layer is sensitive to the surface area, and appears to approach its thermodynamic limit for surface areas of 400σ2 for a system of 4080 molecules. The density profile can be represented by a hyperbolic tangent of an appropriately scaled height. The thickness of the surface is of the order of two molecular diameters at temperatures near the triple point and increases rapidly as the critical point is approached. The computed surfacetens ions agree well with those calculated by statistical perturbation theory.Monte Carlo and Molecular Dynamic simulation of a binary mixture shows clearly the adsorption of the component of higher vapour pressure; the amount absorbed agrees with that calculated from Gibbs's isotherm.
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TL;DR: In this paper, a new generalization of the linear theory of spinodal decomposition is formulated and by considering a "nearly uniform" fluid, some useful results for the long-wavelength behaviour of the liquid structure factor of various monatomic liquids are obtained.
Abstract: Recent theoretical work on the microscopic structure and surface tension of the liquid-vapour interface of simple (argon-like) fluids is critically reviewed. In particular, the form of pairwise intermolecular correlations in the liquid surface and the capillary wave treatment of the interface are examined in some detail. It is argued that conventional capillary wave theory, which leads to divergences in the width of the density profile, is unsatisfactory for describing all the equilibrium aspects of the interface. The density functional formalism which has been developed to study the liquid-vapour interface can also be profitably applied to other problems in the statistical mechanics of non-uniform fluids; here a new generalization of the ‘linear’ theory of spinodal decomposition is formulated and by considering a ‘nearly uniform’ fluid, some useful results for the long-wavelength behaviour of the liquid structure factor of various monatomic liquids are obtained. Some other topics of current inte...
2,202 citations
01 Jan 1979
TL;DR: In this paper, it is shown that the mutual interaction between the three materials in the immediate vicinity of a contact line can significantly affect the statics as well as the dynamics of an entire flow field.
Abstract: A contact line is formed at the intersection of two immiscible fluids and a solid. That the mutual interaction between the three materials in the immediate vicinity of a contact line can significantly affect the statics as well as the dynamics of an entire flow field is demonstrated by the behavior of two immiscible fluids in a capillary. It is well known that the height to which a column of liquid will rise in a vertical circular capillary with small radius, a, whose lower end is placed into a bath, is given by (2(j/apg) cos (), where (j is the surface tension of the air/liquid interface, f) is the static contact angle as measured from the liquid side of the contact line, p is the density, and g is the magnitude of the accelera tion due to gravity.! Thus, depending on the value of the contact angle, e, which is a direct consequence of the molecular interactions among the three materials at the contact line, the height can take on any value within the interval [ 2(J/apg, 2(J/apg]. In a sense, the influence of the contact angle is indirect: the contact angle, in capillaries with small radii, controls the radius of curvature of the meniscus which, in turn, regulates the pressure in the liquid under the meniscus. It is this pressure that determines the height of the column. In a similar manner, the dynamic contact angle can influence the rate of displacement of tbe meniscus through the capillary. The pressure drop
1,169 citations
TL;DR: In this paper, a computer-simulation study of homogeneous gas-liquid nucleation in a Lennard-Jones system was performed using umbrella sampling, and the free energy of a cluster was computed as a function of its size.
Abstract: We report a computer-simulation study of homogeneous gas–liquid nucleation in a Lennard-Jones system. Using umbrella sampling, we compute the free energy of a cluster as a function of its size. A thermodynamic integration scheme is employed to determine the height of the nucleation barrier as a function of supersaturation. Our simulations illustrate that the mechanical and the thermodynamical surfaces of tension and surface tension differ significantly. In particular, we show that the mechanical definition of the surface tension cannot be used to compute this barrier height. We find that the relations recently proposed by McGraw and Laaksonen [J. Chem. Phys. 106, 5284 (1997)] for the height of the barrier and for the size of the critical nucleus are obeyed.
447 citations
TL;DR: In this paper, the authors show that observed disagreement between simulation results is due to the fact that different authors inadvertently simulated different model fluids, which results in different results for coexistence properties (orthobaric densities, normal and tangential pressure profiles, and surface tension).
Abstract: Canonical molecular dynamics (MD) and Monte Carlo (MC) simulations for liquid/vapor equilibrium in truncated Lennard-Jones fluid have been carried out. Different results for coexistence properties (orthobaric densities, normal and tangential pressure profiles, and surface tension) have been reported in each method. These differences are attributed in literature to different set up conditions, e.g., size of simulation cell, number of particles, cut-off radius, time of simulations, etc., applied by different authors. In the present study we show that observed disagreement between simulation results is due to the fact that different authors inadvertently simulated different model fluids. The origin of the problem lies in details of truncation procedure used in simulation studies. Care has to be exercised in doing the comparison between both methods because in MC calculations one deals with the truncated potential, while in MD calculations one uses the truncated forces, i.e., derivative of the potential. The truncated force does not uniquely define the primordial potential. It results in MD and MC simulations being performed for different potential models. No differences in the coexistence properties obtained from MD and MC simulations are found when the same potential model is used. An additional force due to the discontinuity of the truncated potential at cut-off distance becomes crucial for inhomogeneous fluids and has to be included into the virial calculations in MC and MD, and into the computation of trajectories in MD simulations. The normal pressure profile for the truncated potential is constant through the interface and both vapor and liquid regions only when this contribution is taken into account, and ignoring it results in incorrect value of surface tension.
438 citations
TL;DR: Gelb et al. as mentioned in this paper used the Barrett−Joyner−Halenda (BJH) method to yield pore size distributions, which are tested against exact pore sizes directly measured from the pore structures.
Abstract: We have prepared a series of molecular models of porous glass using a recently developed procedure (Gelb, L. D.; Gubbins, K. E. Langmuir 1998, 14, 2097) that mimics the experimental processes that produce Vycor and controlled-pore glasses. We calculate nitrogen adsorption isotherms in these precisely characterized model glasses using Monte Carlo simulations. These isotherms are analyzed using the Barrett−Joyner−Halenda (BJH) method to yield pore size distributions, which are tested against exact pore size distributions directly measured from the pore structures. The BJH method yields overly sharp distributions that are systematically shifted (by about 1 nm) to lower pore sizes than those from our geometric method.
430 citations