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Anisotropic molecular diffusion in confinement I: Transport of small particles in potential and density gradients

Höllring, Kevin; Baer, Andreas; Vučemilović-Alagić, Nataša; Smith, David M.; Smith, Ana-Sunčana (2023) Anisotropic molecular diffusion in confinement I: Transport of small particles in potential and density gradients. Journal of Colloid and Interface Science, 650 . pp. 1930-1940. ISSN 00219797

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Hypothesis: Diffusion in confinement is an important fundamental problem with significant implications for applications of supported liquid phases. However, resolving the spatially dependent diffusion coefficient, parallel and perpendicular to interfaces, has been a standing issue. In the vicinity of interfaces, density fluctuations as a consequence of layering locally impose statistical drift, which impedes the analysis of spatially dependent diffusion coefficients even further. We hypothesise, that we can derive a model to spatially resolve interfaceperpendicular diffusion coefficients based on local lifetime statistics with an extension to explicitly account for the effect of local drift using the Smoluchowski equation, that allows us to resolve anisotropic and spatially dependent diffusivity landscapes at interfaces. Methods and simulations: An analytic relation between local crossing times in system slices and diffusivity as well as an explicit term for calculating drift-induced systematic errors is presented. The method is validated on Molecular Dynamics simulations of bulk water and applied to simulations of water in slit pores. Findings: After validation on bulk liquids, we clearly demonstrate the anisotropic nature of diffusion coefficients at interfaces. Significant spatial variations in the diffusivities correlate with interface-induced structuring but cannot be solely attributed to the drift induced by local density fluctuations.

Item Type: Article
Uncontrolled Keywords: Transport coefficient; Diffusion in pores; Porous materials; Anisotropic diffusion; Diffusion at interfaces; Drift and density gradient;
Divisions: Division of Physical Chemistry
Depositing User: Ana Sunčana Smith
Date Deposited: 18 Aug 2023 13:33
DOI: 10.1016/j.jcis.2023.07.088

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