Asymptotic methods for confined fluids

The thermodynamics and microstructure of confined fluids with small particle number are best described using the canonical ensemble. However, practical calculations can usually only be performed in the grand-canonical ensemble, which can introduce unphysical artifacts. We employ the method of asymptotics to transform grand-canonical observables to the canonical ensemble, where the former can be conveniently obtained using the classical density functional theory of inhomogeneous fluids. By formulating the ensemble transformation as a contour integral in the complex fugacity plane we reveal the influence of the Yang-Lee zeros in determining the form and convergence properties of the asymptotic series. The theory is employed to develop expansions for the canonical partition function and the canonical one-body density. Numerical investigations are then performed using an exactly soluble one-dimensional model system of hard rods.

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Publication Details

Journal
Physical review. E
Published
2025-02-28
DOI
https://doi.org/10.1103/physreve.111.024144
Primary Topic
Advanced Thermodynamics and Statistical Mechanics
Type
article
Field-Weighted Citation Impact
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article

Asymptotic methods for confined fluids

J. M. Brader, Emmanuel di Bernardo
Physical review. E
Advanced Thermodynamics and Statistical Mechanics
article

Asymptotic methods for confined fluids

J. M. Brader, Emmanuel di Bernardo
article en

Abstract

The thermodynamics and microstructure of confined fluids with small particle number are best described using the canonical ensemble. However, practical calculations can usually only be performed in the grand-canonical ensemble, which can introduce unphysical artifacts. We employ the method of asymptotics to transform grand-canonical observables to the canonical ensemble, where the former can be conveniently obtained using the classical density functional theory of inhomogeneous fluids. By formulating the ensemble transformation as a contour integral in the complex fugacity plane we reveal the influence of the Yang-Lee zeros in determining the form and convergence properties of the asymptotic series. The theory is employed to develop expansions for the canonical partition function and the canonical one-body density. Numerical investigations are then performed using an exactly soluble one-dimensional model system of hard rods.

Physical review. EVol. 111(2)
University of Fribourg (CH)
Openalex Percentile: Top 97%
Advanced Thermodynamics and Statistical Mechanics
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