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2
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36849122972
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The idea of considering the different effects of attractive and repulsive forces is embedded in the van der Waals equation and motivated the development of perturbation theories of liquids. For important early work see, e.g.
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(1954)
J. Chem. Phys.
, vol.22
, pp. 1420
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Zwanzig, R.1
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10
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0000910155
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For a general review, see, C. Domb, J. L. Lebowitz, Academic, New York
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(1992)
Phase Transitions and Critical Phenomena,
, vol.14
, pp. 136
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Forgacs, G.1
Lipowsky, R.2
Nieuwenhuizen, Th. M.3
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15
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84927492065
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MD simulations were carried out under fixed N,V,T (number of particles, volume, temperature) conditions with periodic boundary conditions in the x,y directions and bounded by walls in the z direction. The box size was 22.5σ on a side. The LJ potential was truncated at 2.5σ. For the densities under consideration N fell in the range ≈5000–10 000. Simulations were carried out for both the Lennard-Jones and repulsive reference potentials at T=1.35 for a range of densities.
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16
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84927497209
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In the usual density functional approach, attractive interactions are analyzed using a crude approximation where the inhomogeneous pair correlation function is replaced by a product of singlet functions [c9]. Such inconsistent approximations used for the attractive interactions “contaminate” the description of the repulsive forces and reduce the accuracy of the overall theory.
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21
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84927468620
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Simulations for N=3000 particles at T=0.60 and T=1.0 were carried out. The former is very slightly below the triple point ( T=0.61) for the truncated LJ potential. A box size up to 10×10×90σ, the largest dimension being normal to the interface, was used. A small field was applied to the LJ system to stop any slight center of gravity drift.
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22
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84927483639
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The mean field theory consistently underestimates the vapor density. This can be understood from the underestimation of correlations implied by the use of Eq. 2 at low density. This in turn affects the mean field prediction for the coexisting bulk liquid density.
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23
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84927475057
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This is the same procedure used in uniform fluids. In that case the calculation of the inhomogeneous force field is trivial. Then the structure of the reference fluid in the presence of that (vanishing) force field is calculated using as accurate a theory as possible.
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