Effect of structural considerations on the development of free energy functionals for the square-well fluid

• Published in: Molecular physics Vol. 116; no. 15-16; pp. 1977 - 1989
• Main Authors: Bernet, Thomas, Piñeiro, Manuel M., Plantier, Frédéric, Miqueu, Christelle
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis 18-08-2018; Taylor & Francis Ltd
• Subjects: Approximation; Chemical Sciences; coarse-graining; Criteria; Density functional theory; Engineering Sciences; Free energy; fundamental-measure theory; Mathematical analysis; mean-field; or physical chemistry; pair correlation function; Physics; Sum rules; Theoretical and; Density functional theory; pair correlation function; fundamental-measure theory; coarse-graining; mean-field
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2018.1438677

In this work, we compare four inhomogeneous square-well fluid models, only distinct in the approximation on the pair correlation function present in the attractive free energy term of the density functional theory (DFT). Various criteria can be considered to select or validate an approximation, depending on fundamental interests or for a specified application. Here the considered criteria of selection were the verification of sum rules, and the prediction of both the adsorbed quantity and the density profiles. Even if a model satisfies one of these criteria, it may fail to describe others, so they can be considered supplementary to each other and in no case redundant. According to this study, one can attach more importance to any of these criteria depending on the specific objectives intended for the model development and purpose. They can serve as references in the development of new DFT models, eventually with other criteria, according to the objective of the work and the accuracy desired.