Drying and wetting transitions of a Lennard-Jones fluid: Simulations and density functional theory

Robert Evans, Maria Stewart, Nigel B. Wilding

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Abstract


We report a theoretical and simulation study of the drying and wetting phase transitions of a truncated Lennard-Jones fluid at a flat structureless wall. Binding potential calculations predict that the nature of these transitions depends on whether the wall-fluid attraction has a long ranged (LR) power law decay or is instead truncated, rendering it short ranged (SR). Using grand canonical Monte Carlo simulation and classical density functional theory, we examine both cases in detail. We find that for the LR case wetting is first order, while drying is continuous (critical) and occurs exactly at zero attractive wall strength, i.e., in the limit of a hard wall. In the SR case, drying is also critical but the order of the wetting transition depends on the truncation range of the wall-fluid potential. We characterize the approach to critical drying and wetting in terms of the density and local compressibility profiles and via the finite- size scaling properties of the probability distribution of the overall density. For the LR case, where the drying point is known exactly, this analysis allows us to estimate the exponent ν∥, which controls the parallel correlation length, i.e., the extent of vapor bubbles at the wall. Surprisingly, the value we obtain is over twice that predicted by mean field and renormalization group calculations, despite the fact that our three dimensional system is at the upper critical dimension where mean field theory for critical exponents is expected to hold. Possible reasons for this discrepancy are discussed in the light of fresh insights into the nature of near critical finite-size effects.
Original languageEnglish
Article number044701
Number of pages20
JournalJournal of Chemical Physics
Volume147
Issue number4
Early online date25 Jul 2017
DOIs
Publication statusPublished - 28 Jul 2017

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drying
wetting
Density functional theory
Wetting
Drying
density functional theory
Fluids
fluids
simulation
Mean field theory
exponents
Compressibility
Density (specific gravity)
Probability distributions
Phase transitions
compressibility
attraction
Vapors
bubbles
vapors

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Drying and wetting transitions of a Lennard-Jones fluid: Simulations and density functional theory. / Evans, Robert; Stewart, Maria; Wilding, Nigel B.

In: Journal of Chemical Physics, Vol. 147, No. 4, 044701, 28.07.2017.

Research output: Contribution to journalArticle

Evans, Robert ; Stewart, Maria ; Wilding, Nigel B. / Drying and wetting transitions of a Lennard-Jones fluid: Simulations and density functional theory. In: Journal of Chemical Physics. 2017 ; Vol. 147, No. 4.
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