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单电荷壁处的抗衡离子:求和规则。

Counter-ions at single charged wall: Sum rules.

作者信息

Samaj Ladislav

机构信息

Institute of Physics, Slovak Academy of Sciences, Dúbravská cesta 9, 845 11, Bratislava, Slovakia,

出版信息

Eur Phys J E Soft Matter. 2013 Sep;36(9):100. doi: 10.1140/epje/i2013-13100-6. Epub 2013 Sep 19.

DOI:10.1140/epje/i2013-13100-6
PMID:24045984
Abstract

For inhomogeneous classical Coulomb fluids in thermal equilibrium, like the jellium or the two-component Coulomb gas, there exists a variety of exact sum rules which relate the particle one-body and two-body densities. The necessary condition for these sum rules is that the Coulomb fluid possesses good screening properties, i.e. the particle correlation functions or the averaged charge inhomogeneity, say close to a wall, exhibit a short-range (usually exponential) decay. In this work, we study equilibrium statistical mechanics of an electric double layer with counter-ions only, i.e. a globally neutral system of equally charged point-like particles in the vicinity of a plain hard wall carrying a fixed uniform surface charge density of opposite sign. At large distances from the wall, the one-body and two-body counter-ion densities go to zero slowly according to the inverse-power law. In spite of the absence of screening, all known sum rules are shown to hold for two exactly solvable cases of the present system: in the weak-coupling Poisson-Boltzmann limit (in any spatial dimension larger than one) and at a special free-fermion coupling constant in two dimensions. This fact indicates an extended validity of the sum rules and provides a consistency check for reasonable theoretical approaches.

摘要

对于处于热平衡的非均匀经典库仑流体,如电子气或双组分库仑气体,存在多种精确的求和规则,这些规则将粒子的单体和二体密度联系起来。这些求和规则的必要条件是库仑流体具有良好的屏蔽特性,即粒子关联函数或平均电荷不均匀性(例如靠近壁处)呈现短程(通常为指数)衰减。在这项工作中,我们研究仅含反离子的电双层的平衡统计力学,即一个全局中性系统,其中等电荷的点状粒子位于带有固定均匀异号表面电荷密度的平面硬壁附近。在远离壁的地方,单体和二体反离子密度根据反幂律缓慢趋于零。尽管缺乏屏蔽,但对于本系统的两个精确可解情况,所有已知的求和规则都被证明成立:在弱耦合泊松 - 玻尔兹曼极限下(在任何大于一维的空间维度中)以及在二维中的一个特殊自由费米子耦合常数下。这一事实表明求和规则具有更广泛的有效性,并为合理的理论方法提供了一致性检验

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本文引用的文献

1
Electrostatics in soft matter.软物质中的静电学
J Phys Condens Matter. 2009 Mar 18;21(11):113102. doi: 10.1088/0953-8984/21/11/113102. Epub 2009 Feb 17.
2
Counter-ions at charged walls: two-dimensional systems.带电壁上的抗衡离子:二维系统
Eur Phys J E Soft Matter. 2011 Feb;34(2):20. doi: 10.1140/epje/i2011-11020-1. Epub 2011 Feb 28.
3
One-dimensional counterion gas between charged surfaces: exact results compared with weak- and strong-coupling analyses.带电表面之间的一维抗衡离子气体:精确结果与弱耦合和强耦合分析的比较
J Chem Phys. 2009 Mar 7;130(9):094504. doi: 10.1063/1.3078492.
4
Test-charge theory for the electric double layer.电双层的测试电荷理论。
Phys Rev E Stat Nonlin Soft Matter Phys. 2004;70(1 Pt 2):016102. doi: 10.1103/PhysRevE.70.016102. Epub 2004 Jul 1.
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Effective interactions between electric double layers.双电层之间的有效相互作用。
Annu Rev Phys Chem. 2000;51:209-42. doi: 10.1146/annurev.physchem.51.1.209.