Weighted density-functional theory for simple fluids; prewetting of a Lennard-Jones fluid

M.B. Sweatman

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Abstract

The prewetting of a Lennard-Jones fluid is studied using weighted density-functional theory. The intrinsic Helmholtz free-energy functional is separated into repulsive and attractive contributions. An accurate functional for hard spheres is used for the repulsive functional and a weighted density-functional method is used for the attractive part. The results for this theory are compared against mean-field density-functional theory, the theory of Velasco and Tarazona [E. Velasco and P. Tarazona, J. Chem. Phys. 91, 7916 (1989)] and grand canonical ensemble simulation results. The results demonstrate that the weighted density functional for attractive forces may offer a significant increase in accuracy over the other theories. The density-functional and simulation results also indicate that a previous estimate of the wetting temperature for a model of the interaction of argon with solid carbon dioxide, obtained from simulations [J. E. Finn and P. A. Monson, Phys. Rev. A, 39, 6402 (1989)], is incorrect. The weighted density-functional method indicates that triple-point prewetting is observed for this model potential.
LanguageEnglish
Pages011102
JournalPhysical Review E: Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics
Volume65
Issue number1
DOIs
Publication statusPublished - Jan 2001

Fingerprint

Lennard-Jones
Density Functional
density functional theory
Fluid
fluids
simulation
wetting
carbon dioxide
Triple Point
Simulation
Canonical Ensemble
free energy
argon
Wetting
Hermann Von Helmholtz
Hard Spheres
Energy Functional
Carbon Dioxide
Mean Field
Free Energy

Keywords

  • density
  • fluids
  • prewetting
  • chemical engineering

Cite this

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abstract = "The prewetting of a Lennard-Jones fluid is studied using weighted density-functional theory. The intrinsic Helmholtz free-energy functional is separated into repulsive and attractive contributions. An accurate functional for hard spheres is used for the repulsive functional and a weighted density-functional method is used for the attractive part. The results for this theory are compared against mean-field density-functional theory, the theory of Velasco and Tarazona [E. Velasco and P. Tarazona, J. Chem. Phys. 91, 7916 (1989)] and grand canonical ensemble simulation results. The results demonstrate that the weighted density functional for attractive forces may offer a significant increase in accuracy over the other theories. The density-functional and simulation results also indicate that a previous estimate of the wetting temperature for a model of the interaction of argon with solid carbon dioxide, obtained from simulations [J. E. Finn and P. A. Monson, Phys. Rev. A, 39, 6402 (1989)], is incorrect. The weighted density-functional method indicates that triple-point prewetting is observed for this model potential.",
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N2 - The prewetting of a Lennard-Jones fluid is studied using weighted density-functional theory. The intrinsic Helmholtz free-energy functional is separated into repulsive and attractive contributions. An accurate functional for hard spheres is used for the repulsive functional and a weighted density-functional method is used for the attractive part. The results for this theory are compared against mean-field density-functional theory, the theory of Velasco and Tarazona [E. Velasco and P. Tarazona, J. Chem. Phys. 91, 7916 (1989)] and grand canonical ensemble simulation results. The results demonstrate that the weighted density functional for attractive forces may offer a significant increase in accuracy over the other theories. The density-functional and simulation results also indicate that a previous estimate of the wetting temperature for a model of the interaction of argon with solid carbon dioxide, obtained from simulations [J. E. Finn and P. A. Monson, Phys. Rev. A, 39, 6402 (1989)], is incorrect. The weighted density-functional method indicates that triple-point prewetting is observed for this model potential.

AB - The prewetting of a Lennard-Jones fluid is studied using weighted density-functional theory. The intrinsic Helmholtz free-energy functional is separated into repulsive and attractive contributions. An accurate functional for hard spheres is used for the repulsive functional and a weighted density-functional method is used for the attractive part. The results for this theory are compared against mean-field density-functional theory, the theory of Velasco and Tarazona [E. Velasco and P. Tarazona, J. Chem. Phys. 91, 7916 (1989)] and grand canonical ensemble simulation results. The results demonstrate that the weighted density functional for attractive forces may offer a significant increase in accuracy over the other theories. The density-functional and simulation results also indicate that a previous estimate of the wetting temperature for a model of the interaction of argon with solid carbon dioxide, obtained from simulations [J. E. Finn and P. A. Monson, Phys. Rev. A, 39, 6402 (1989)], is incorrect. The weighted density-functional method indicates that triple-point prewetting is observed for this model potential.

KW - density

KW - fluids

KW - prewetting

KW - chemical engineering

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