Examination of inconsistencies in the physical modeling of vapor-liquid interfaces of strongly non-ideal mixtures
File(s)
Accepted version
Author(s)
Fleckenstein, Florian
Wagner, Max
Bernet, Thomas
Muller, Erich
Simon, Stephan
Type
Journal Article
Abstract
The accurate modeling of fluid interfaces is crucial in numerous scientific and engineering applications. Different physical models such as molecular simulation (MS), density functional theory (DFT), and density gradient theory (DGT) are usually employed for this purpose. However, recent findings have highlighted discrepancies in interfacial structure predictions, particularly for strongly non-ideal azeotropic systems [Fluid Phase Equilib., 2023, 564, 113596]. Specifically, DGT was observed to produce spurious interfacial profiles that deviated significantly from those obtained from MS. This study systematically investigates these inconsistencies by performing a comparative in depth analysis of MS, DFT, and DGT for eight binary alkane + alcohol azeotropic systems. The unusual topology of the interfacial structure is confirmed by all three methods, although important quantitative differences are observed. Possible reasons for these inconsistencies are discussed.
Date Issued
2025-11-28
Date Acceptance
2025-10-21
Citation
Physical Chemistry, Chemical Physics - PCCP, 2025, 27 (44), pp.23966-23985
ISSN
1463-9076
Publisher
Royal Society of Chemistry
Start Page
23966
End Page
23985
Journal / Book Title
Physical Chemistry, Chemical Physics - PCCP
Volume
27
Issue
44
Copyright Statement
© Royal Society of Chemistry. This is the author’s accepted manuscript made available under a CC-BY licence in accordance with Imperial’s Research Publications Open Access policy (www.imperial.ac.uk/oa-policy)
License URL
Publication Status
Published
Date Publish Online
2025-10-29