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Density Fluctuations of Hard-Sphere Fluids in Narrow Confinement

Journal article
Authors Kim Nygård
Sten Sarman
Kristin Hyltegren
Shirish Chodankar
Edith Perret
Johan Buitenhuis
J Friso van der Veen
Roland Kjellander
Published in Physical Review X
Volume 6
Issue 1
Pages artikel nr 011014
ISSN 2160-3308
Publication year 2016
Published at Department of Chemistry and Molecular Biology
Pages artikel nr 011014
Language en
Keywords Colloid dispersion, liquid structure, confined fluid, pair distribution, density fluctuations, integral equation theory, SAXS, x-ray scattering
Subject categories Condensed Matter Physics, Surfaces and interfaces, Liquid physics, Mesoscopic physics, Physical Chemistry, Surface and colloid chemistry, Chemical physics, Theoretical Chemistry, Statistical mechanics


Spatial confinement induces microscopic ordering of fluids, which in turn alters many of their dynamic and thermodynamic properties. However, the isothermal compressibility has hitherto been largely overlooked in the literature, despite its obvious connection to the underlying microscopic structure and density fluctuations in confined geometries. Here, we address this issue by probing density profiles and structure factors of hard-sphere fluids in various narrow slits, using x-ray scattering from colloid-filled nanofluidic containers and integral-equation-based statistical mechanics at the level of pair distributions for inhomogeneous fluids. Most importantly, we demonstrate that density fluctuations and isothermal compressibilities in confined fluids can be obtained experimentally from the long-wavelength limit of the structure factor, providing a formally exact and experimentally accessible connection between microscopic structure and macroscopic, thermodynamic properties. Our approach will thus, for example, allow direct experimental verification of theoretically predicted enhanced density fluctuations in liquids near solvophobic interfaces.

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