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非等温反应扩散系统中的浓度波动

Concentration fluctuations in nonisothermal reaction-diffusion systems.

作者信息

Ortiz de Zárate José M, Sengers Jan V, Bedeaux Dick, Kjelstrup Signe

机构信息

Departamento de Física Aplicada I, Universidad Complutense, 28040 Madrid, Spain.

出版信息

J Chem Phys. 2007 Jul 21;127(3):034501. doi: 10.1063/1.2746326.

Abstract

In this paper a simple reaction-diffusion system, namely a binary fluid mixture with an association-dissociation reaction between the two components, is considered. Fluctuations at hydrodynamic spatiotemporal scales when a temperature gradient is present in this chemically reacting system are studied. First, fluctuating hydrodynamics when the system is in global equilibrium (isothermal) is reviewed. Comparing the two cases, an enhancement of the intensity of concentration fluctuations in the presence of a temperature gradient is predicted. The nonequilibrium concentration fluctuations are spatially long ranged, with an intensity depending on the wave number q. The intensity exhibits a crossover from a proportional, variantq(-4) to a proportional, variantq(-2) behavior depending on whether the corresponding wavelength is smaller or larger than the penetration depth of the reacting mixture. This opens a possibility to distinguish between diffusion- or activation-controlled regimes of the reaction by measuring these fluctuations. In addition, the possible observation of these fluctuations in nonequilibrium molecular dynamics simulations is considered.

摘要

本文考虑了一个简单的反应扩散系统,即一种二元流体混合物,其两种组分之间存在缔合 - 解离反应。研究了在这个化学反应系统中存在温度梯度时流体动力学时空尺度上的涨落。首先,回顾了系统处于全局平衡(等温)时的涨落流体动力学。比较这两种情况,预测了在存在温度梯度时浓度涨落强度的增强。非平衡浓度涨落具有空间长程性,其强度取决于波数q。根据相应波长是小于还是大于反应混合物的穿透深度,强度表现出从与q(-4)成比例变化到与q(-2)成比例变化的转变。这为通过测量这些涨落来区分反应的扩散控制或活化控制机制提供了可能性。此外,还考虑了在非平衡分子动力学模拟中对这些涨落进行观测的可能性。

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