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Coupling of sedimentation and liquid structure: Influence on hard sphere nucleation

Research output: Contribution to journalArticle

Original languageEnglish
Article number204506
Number of pages7
JournalJournal of Chemical Physics
Issue number20
Early online date30 Nov 2018
DateAccepted/In press - 29 Oct 2018
DateE-pub ahead of print - 30 Nov 2018
DatePublished (current) - 30 Nov 2018


The discrepancy in nucleation rate densities between simulated and experimental hard spheres remains staggering and unexplained. Suggestively, more strongly sedimenting colloidal suspensions of hard spheres nucleate much faster than weakly sedimenting systems. In this work, we consider first the effect of sedimentation on the structure of colloidal hard spheres by tuning the density mismatch between solvent and colloidal particles. In particular, we investigate the effect on the degree of the fivefold symmetry present. Second, we study the size of density fluctuations in these experimental systems in comparison to simulations. The density fluctuations are measured by assigning each particle a local density, which is related to the number of particles within a distance of 3.25 particle diameters. The standard deviation of these local densities gives an indication of the fluctuations present in the system. Fivefold symmetry is suppressed by a factor of two when sedimentation is induced in our system. Density fluctuations are increased by a factor of two in experiments compared to simulations. The change in fivefold symmetry makes a difference to the expected nucleation rates, but we demonstrate that it is ultimately too small to resolve the discrepancy between experiment and simulation, while the fluctuations are shown to be an artefact of 3d particle tracking.

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    Rights statement: This is the accepted author manuscript (AAM). The final published version (version of record) is available online via AIP at DOI: 10.1063/1.5050397. Please refer to any applicable terms of use of the publisher.

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