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J Phys Chem B. 2005 Mar 31;109(12):5824-35.

The Stokes-Einstein relationship and the levitation effect: size-dependent diffusion maximum in dense fluids and close-packed disordered solids.

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1
Solid State and Structural Chemistry Unit and Center for Condensed Matter Theory, Indian Institute of Science, Bangalore 560012, India.

Abstract

We report a molecular dynamics study of a binary mixture consisting of a large (host) particle and a smaller (guest) particle whose radius is varied over a range. These simulations investigate the possible existence of a diffusion anomaly or levitation effect in dense fluids, previously seen for guest molecules diffusing within porous solids. The voids in the larger component have been characterized in terms of void and neck distributions by means of Voronoi polyhedral analysis. Four different mixtures with differing ratios of guest to host diffusivities (D) have been studied. The results suggest that the diffusion anomaly is seen in both close-packed solids with disorder and dense fluids. In the latter, the void network is constantly and dynamically changing and possesses a considerable degree of disorder. The two regimes, viz., the linear regime (LR) and the anomalous regime (AR), found for porous solids are shown to exist for a dense medium as well. The linear regime is characterized by D(g) proportional to 1/sigma(gg)(2), where sigma(gg) is the diameter of the guest. The anomalous regime exhibits a maximum in D up to rather high temperatures (T = 1.663), even though in porous solids the maximum disappears at higher temperatures. In agreement with previous studies on porous solids, a particle in the AR is associated with lower activation energy, lower friction, and less backscattering in the velocity autocorrelation function when compared to a particle in the LR. Wavevector dependent self-diffusivity, Delta, and decay of the intermediate scattering function, F(s)(k, t), exhibit contrasting behaviors for the LR and AR. For LR, Delta exhibits a minimum at values of k at which there are spatial correlations in S(k) while a smooth decrease with k is seen for AR. For LR, F(s)(k, t) shows a biexponential decay corresponding to two different time scales of motion. Probably, the fast decay is associated with motion within the first shell of solvent neighbors and the slow decay with motion past these shells. For AR, a single-exponential decay is seen. The results indicate a breakdown of the Stokes-Einstein (SE) relationship. The relevant quantity that determines the validity of the SE relationship is the levitation parameter which is indirectly related to the solute/solvent radius ratio and not either the size of the solute or the solvent alone.

PMID:
16851635
DOI:
10.1021/jp046312w
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