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通过非均匀纳米孔的单分子扩散。

Single-file diffusion through inhomogeneous nanopores.

作者信息

Bandyopadhyay Tusar

机构信息

Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Trombay, Mumbai, India.

出版信息

J Chem Phys. 2008 Mar 21;128(11):114712. doi: 10.1063/1.2894839.

Abstract

Strict one-dimensional diffusion, due to geometrical confinement in a nanopore, of an assembly of particles forbids overtaking by each other, giving rise to single-file diffusion (SFD). Smooth carbon nanotube is the epitome of SFD. However, natural nanoporous materials are far from smooth; morphologically, the nanopores' inner surface may provide an inhomogeneous environment for diffusion to occur, giving rise to subnormal diffusion even for an isolated particle diffusing through this fractal landscape. The realm of fractional diffusion (FD) falls under this paradigm. In order to understand the characteristics of SFD through inhomogeneous nanopores, here, we introduce a fractional SFD (FSFD) formalism that deals with a combination of these two phenomena, namely, SFD of particles, each of which are moving subdiffusively in one dimension. For an infinite system, we obtain the mean square displacement (MSD) of the combined entity and our analysis is based on FD equation for particles moving in concert where the single-file correlation is established through reflection principle. For a finite system, we calculate the transport probabilities based on continuous time random walk model. While both the diffusion mechanisms (SFD and FD) acting separately are responsible for slow dynamics at long times, their combined effect leads to ultraslow diffusion. For example, while the long time asymptote of MSD of SFD scales as sqr rt of t, that for FSFD is sqr rt of t(alpha), where alpha is the measure of the extent of inhomogeneity. These findings, which are believed to occur in a natural inhomogeneous nanopore, is also important for design and fabrication of nanofluidic devices through which the fluid delivery can be engineered.

摘要

由于纳米孔中的几何限制,粒子集合的严格一维扩散禁止粒子相互超越,从而产生单文件扩散(SFD)。光滑的碳纳米管是SFD的典型代表。然而,天然纳米多孔材料远非光滑;从形态学上讲,纳米孔的内表面可能为扩散提供不均匀的环境,即使对于单个粒子在这种分形景观中扩散也会导致亚正常扩散。分数扩散(FD)领域就属于这一范式。为了通过不均匀纳米孔理解SFD的特性,在此,我们引入一种分数SFD(FSFD)形式体系,它处理这两种现象的组合,即粒子的SFD,每个粒子在一维中进行亚扩散运动。对于无限系统,我们获得组合实体的平均平方位移(MSD),并且我们的分析基于粒子协同运动的FD方程,其中单文件相关性通过反射原理建立。对于有限系统,我们基于连续时间随机游走模型计算传输概率。虽然单独起作用的两种扩散机制(SFD和FD)在长时间导致缓慢动力学,但它们的联合效应导致超慢扩散。例如,虽然SFD的MSD的长时间渐近线按t的平方根缩放,但FSFD的则按t(α)的平方根缩放,其中α是不均匀程度的度量。这些发现在天然不均匀纳米孔中被认为会出现,对于设计和制造纳米流体装置也很重要,通过该装置可以设计流体输送。

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