Uniform distributions in nonuniform systems: Wall potentials generating constant density profiles in classical density functional theory

We study the inverse problem of classical density functional theory for inhomogeneous fluids: finding the wall potential that produces a constant equilibrium density profile, i.e., a perfectly flat density distribution in the accessible region adjacent to a substrate. Within Rosenfeld's fundamental measure theory, we solve this problem for a one-component fluid in planar, spherical, and cylindrical geometries, considering both a hard-sphere fluid and a fluid with an additional truncated Lennard-Jones attraction treated at the mean-field level. Explicit analytical expressions are obtained for planar walls, while spherical walls also admit an analytical treatment in a more cumbersome form. The cylindrical case is treated numerically. The construction provides an explicit microscopic realization of structure-cancelling wall fields related to flat-profile conditions that occur under special matching conditions in interfacial theories of wetting and drying. The theory also yields a compact collection of formulas for weighted densities and one-body direct correlation functions in the three fundamental geometries, providing useful reference expressions for density-functional implementations. The resulting analytic wall potentials are validated in independent density functional calculations, which confirm that the prescribed flat profiles are recovered within numerical accuracy.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-06-24
DOI
https://doi.org/10.1063/5.0339352
Primary Topic
Phase Equilibria and Thermodynamics
Type
article
Field-Weighted Citation Impact
0.00

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article

Uniform distributions in nonuniform systems: Wall potentials generating constant density profiles in classical density functional theory

Jiří Janek, Alexandr Malijevský
The Journal of Chemical Physics
Phase Equilibria and Thermodynamics
article

Uniform distributions in nonuniform systems: Wall potentials generating constant density profiles in classical density functional theory

Jiří Janek, Alexandr Malijevský
article en

Abstract

We study the inverse problem of classical density functional theory for inhomogeneous fluids: finding the wall potential that produces a constant equilibrium density profile, i.e., a perfectly flat density distribution in the accessible region adjacent to a substrate. Within Rosenfeld's fundamental measure theory, we solve this problem for a one-component fluid in planar, spherical, and cylindrical geometries, considering both a hard-sphere fluid and a fluid with an additional truncated Lennard-Jones attraction treated at the mean-field level. Explicit analytical expressions are obtained for planar walls, while spherical walls also admit an analytical treatment in a more cumbersome form. The cylindrical case is treated numerically. The construction provides an explicit microscopic realization of structure-cancelling wall fields related to flat-profile conditions that occur under special matching conditions in interfacial theories of wetting and drying. The theory also yields a compact collection of formulas for weighted densities and one-body direct correlation functions in the three fundamental geometries, providing useful reference expressions for density-functional implementations. The resulting analytic wall potentials are validated in independent density functional calculations, which confirm that the prescribed flat profiles are recovered within numerical accuracy.

The Journal of Chemical PhysicsVol. 164(24)
Czech Academy of Sciences, Institute of Chemical Process Fundamentals (CZ), University of Chemistry and Technology, Prague (CZ)
Grantová Agentura České Republiky
Openalex Percentile: Top 12%
Phase Equilibria and Thermodynamics
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