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受限流体中动力学关联的动力学伊辛模型研究:快时间尺度和慢时间尺度的出现。

A kinetic Ising model study of dynamical correlations in confined fluids: emergence of both fast and slow time scales.

机构信息

Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India.

出版信息

J Chem Phys. 2010 Aug 28;133(8):084509. doi: 10.1063/1.3474948.

Abstract

Experiments and computer simulation studies have revealed existence of rich dynamics in the orientational relaxation of molecules in confined systems such as water in reverse micelles, cyclodextrin cavities, and nanotubes. Here we introduce a novel finite length one dimensional Ising model to investigate the propagation and the annihilation of dynamical correlations in finite systems and to understand the intriguing shortening of the orientational relaxation time that has been reported for small sized reverse micelles. In our finite sized model, the two spins at the two end cells are oriented in the opposite directions to mimic the effects of surface that in real system fixes water orientation in the opposite directions. This produces opposite polarizations to propagate inside from the surface and to produce bulklike condition at the center. This model can be solved analytically for short chains. For long chains, we solve the model numerically with Glauber spin flip dynamics (and also with Metropolis single-spin flip Monte Carlo algorithm). We show that model nicely reproduces many of the features observed in experiments. Due to the destructive interference among correlations that propagate from the surface to the core, one of the rotational relaxation time components decays faster than the bulk. In general, the relaxation of spins is nonexponential due to the interplay between various interactions. In the limit of strong coupling between the spins or in the limit of low temperature, the nature of relaxation of the spins undergoes a qualitative change with the emergence of a homogeneous dynamics where decay is predominantly exponential, again in agreement with experiments.

摘要

实验和计算机模拟研究表明,在受限体系中,如反胶束、环糊精空腔和纳米管中的分子的取向弛豫存在丰富的动力学。在这里,我们引入了一种新的有限长一维伊辛模型,以研究有限体系中动力学相关性的传播和湮灭,并理解在小尺寸反胶束中报道的取向弛豫时间缩短的令人着迷的现象。在我们的有限尺寸模型中,两个末端单元的两个自旋指向相反的方向,以模拟实际体系中固定水分子取向相反的表面效应。这会产生相反的极化,从表面向内传播,并在中心产生类似体相的条件。这个模型可以对短链进行解析求解。对于长链,我们使用格劳伯自旋翻转动力学(也使用了 metropolis 单自旋翻转蒙特卡罗算法)对模型进行数值求解。我们表明,该模型很好地再现了实验中观察到的许多特征。由于从表面传播到核心的相关性之间的破坏性干涉,其中一个旋转弛豫时间分量比体相更快地衰减。通常,由于各种相互作用的相互作用,自旋的弛豫是非指数的。在自旋之间的强耦合极限或低温极限下,自旋弛豫的性质发生定性变化,出现主要是指数衰减的均匀动力学,再次与实验结果一致。

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