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Anomalies in the self-diffusion coefficient near the critical point

Cherayil, Binny J (2002) Anomalies in the self-diffusion coefficient near the critical point. In: Journal of Chemical Physics, 116 (19). pp. 8455-8462.


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In this paper we calculate the contribution Ds to the self-diffusion coefficient D0 from the coupling of solute motion to solvent density fluctuations in an infinitely dilute near-critical binary mixture using the methods of fully renormalized kinetic theory in the disconnected approximation. The expression for Ds is found to be similar to mode-coupling expressions for diffusion coefficients in dense or supercooled liquids. As a function of the solvent density rho, and along the critical isotherm, D0 exhibits an anomalous decrease in the vicinity of the critical point that originates in the vanishing of Ds according to the scaling relation Ds~(rho–rho c)2, where rho c is the critical density. An analogous decrease in D0 has recently been observed in the simulations of Drozdov and Tucker [J. Chem. Phys. 114, 4912 (2001)] on a neat liquid of Lennard-Jones particles, and has been ascribed to local density inhomogeneities in the medium.

Item Type: Journal Article
Publication: Journal of Chemical Physics
Publisher: American Institute of Physics
Additional Information: Copyright for this article belongs to American Institute of Physics (AIP).
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 22 Nov 2004
Last Modified: 19 Sep 2010 04:17
URI: http://eprints.iisc.ac.in/id/eprint/2333

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