To explore the curvature dependence of solid–fluid interfacial thermodynamics, we calculate, using Grand Canonical Monte Carlo simulation, the surface free energy for a 2d hard-disk fluid confined in a circular hard container of radius R as a function of the bulk packing fraction η and wall curvature . (The curvature is negative because the surface is concave.) Combining this with our previous data [Martin et al., J. Phys. Chem. B 124, 7938–7947 (2020)] for the positive curvature case (a hard-disk fluid at a circular wall, ), we obtain a complete picture of surface thermodynamics in this system over the full range of positive and negative wall curvatures. Our results show that γ is linear in with a slope that is the same for both positive and negative wall curvatures, with deviations seen only at high negative curvatures (strong confinement) and high density. This observation indicates that the surface thermodynamics of this system is consistent with the predictions of so-called morphometric thermodynamics at both positive and negative curvatures. In addition, we show that classical density functional theory and a generalized scaled particle theory can be constructed that give excellent agreement with the simulation data over most of the range of curvatures and densities. For extremely high curvatures, where only one or two disks can occupy the container at maximum packing, it is possible to calculate γ exactly. In this limit, the simulations and density functional theory calculations are in remarkable agreement with the exact results.
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7 August 2022
Research Article|
August 03 2022
Inside and out: Surface thermodynamics from positive to negative curvature
Special Collection:
Fluids Meet Solids
Seth C. Martin;
Seth C. Martin
(Data curation, Formal analysis, Investigation, Methodology, Project administration, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, University of St. Mary
, Leavenworth, Kansas 66048, USA
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Hendrik Hansen-Goos;
Hendrik Hansen-Goos
(Formal analysis, Methodology, Software, Writing – review & editing)
2
Institute for Theoretical Physics, University of Tübingen
, 72076 Tübingen, Germany
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Roland Roth
;
Roland Roth
(Formal analysis, Investigation, Methodology, Software, Writing – original draft, Writing – review & editing)
2
Institute for Theoretical Physics, University of Tübingen
, 72076 Tübingen, Germany
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Brian B. Laird
Brian B. Laird
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Validation, Visualization, Writing – original draft, Writing – review & editing)
3
Department of Chemistry, University of Kansas
, Lawrence, Kansas 66045, USA
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Fluids Meets Solids.
J. Chem. Phys. 157, 054702 (2022)
Article history
Received:
May 16 2022
Accepted:
July 06 2022
Citation
Seth C. Martin, Hendrik Hansen-Goos, Roland Roth, Brian B. Laird; Inside and out: Surface thermodynamics from positive to negative curvature. J. Chem. Phys. 7 August 2022; 157 (5): 054702. https://doi.org/10.1063/5.0099295
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