科研之友
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摘要
Although classical density functional theory provides reliable predictions for the static properties of simple equilibrium fluids under confinement, a theory of comparative accuracy for the transport coefficients has yet to emerge. Nonetheless, there is evidence that knowledge of how confinement modifies static behavior can aid in forecasting dynamics. Specifically, recent molecular simulation studies have shown that the relationship between excess entropy and self-diffusivity of a bulk equilibrium fluid changes only modestly when the fluid is isothermally confined, indicating that knowledge of the former might allow semi-quantitative predictions of the latter. Do other static measures, such as those that characterize free or available volume, also strongly correlate with single-particle dynamics of confined fluids? Here, we investigate this question for both the single-component hard-sphere fluid and hard-sphere mixtures. Specifically, we use molecular simulations and fundamental measure theory to study these systems at approximately 10(3) equilibrium state points. We examine three different confining geometries (slit pore, square channel, and cylindrical pore) and the effects of particle packing fraction and particle-boundary interactions. Although average density fails to predict some key qualitative trends for the self-diffusivity of confined fluids, we provide strong empirical evidence that a new generalized measure of available volume for inhomogeneous fluids correlates excellently with self-diffusivity across a wide parameter space in these systems, approximately independently of the degree of confinement. An important consequence, which we demonstrate here, is that density functional theory predictions of this static property can be used together with knowledge of bulk fluid behavior to semi-quantitatively estimate the self-diffusion coefficient of confined fluids under equilibrium conditions.
- 出版日期2009-4
