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强耦合理论下的带对称电荷壁之间的抗衡离子:从晶体到流体相。

Strong-coupling theory of counterions between symmetrically charged walls: from crystal to fluid phases.

机构信息

Institute of Physics, Slovak Academy of Sciences, Bratislava, Slovakia.

出版信息

Soft Matter. 2018 May 23;14(20):4040-4052. doi: 10.1039/c8sm00571k.

Abstract

We study thermal equilibrium of classical pointlike counterions confined between symmetrically charged walls at distance d. At very large couplings when the counterion system is in its crystal phase, a harmonic expansion of particle deviations is made around the bilayer positions, with a free lattice parameter determined from a variational approach. For each of the two walls, the harmonic expansion implies an effective one-body potential at the root of all observables of interest in our Wigner strong-coupling expansion. Analytical results for the particle density profile and the pressure are in good agreement with numerical Monte Carlo data, for small as well as intermediate values of d comparable with the Wigner lattice spacing. While the strong-coupling theory is extended to the fluid regime by using the concept of a correlation hole, the Wigner calculations appear trustworthy for all electrostatic couplings investigated. Our results significantly extend the range of accuracy of analytical equations of state for strongly interacting charged planar interfaces.

摘要

我们研究了距离为 d 的对称带电壁之间经典点状抗衡离子的热平衡。在非常大的耦合时,抗衡离子系统处于其晶体相,围绕双层位置进行粒子偏离的谐波展开,晶格参数由变分法确定。对于两个壁中的每一个,谐波展开意味着在我们的维格纳强耦合展开中所有感兴趣的观测值的根源处存在有效的单粒子势。粒子密度分布和压力的解析结果与数值蒙特卡罗数据吻合良好,对于与维格纳晶格间距相当的小和中等距离 d 也是如此。虽然通过关联孔的概念将强耦合理论扩展到流体区域,但对于所研究的所有静电耦合,维格纳计算似乎都是可靠的。我们的结果显著扩展了强相互作用带电平面界面的解析状态方程的精度范围。

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