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随机带电表面的强耦合静电学:抗脆弱性与有效相互作用

Strong coupling electrostatics for randomly charged surfaces: antifragility and effective interactions.

作者信息

Ghodrat Malihe, Naji Ali, Komaie-Moghaddam Haniyeh, Podgornik Rudolf

机构信息

School of Physics, Institute for Research in Fundamental Sciences (IPM), Tehran 19395-5531, Iran.

出版信息

Soft Matter. 2015 May 7;11(17):3441-59. doi: 10.1039/c4sm02846e.

Abstract

We study the effective interaction mediated by strongly coupled Coulomb fluids between dielectric surfaces carrying quenched, random monopolar charges with equal mean and variance, both when the Coulomb fluid consists only of mobile multivalent counterions and when it consists of an asymmetric ionic mixture containing multivalent and monovalent (salt) ions in equilibrium with an aqueous bulk reservoir. We analyze the consequences that follow from the interplay between surface charge disorder, dielectric and salt image effects, and the strong electrostatic coupling that results from multivalent counterions on the distribution of these ions and the effective interaction pressure they mediate between the surfaces. In a dielectrically homogeneous system, we show that the multivalent counterions are attracted towards the surfaces with a singular, disorder-induced potential that diverges logarithmically on approach to the surfaces, creating a singular but integrable counterion density profile that exhibits an algebraic divergence at the surfaces with an exponent that depends on the surface charge (disorder) variance. This effect drives the system towards a state of lower thermal 'disorder', one that can be described by a renormalized temperature, exhibiting thus a remarkable antifragility. In the presence of an interfacial dielectric discontinuity, the singular behavior of counterion density at the surfaces is removed but multivalent counterions are still accumulated much more strongly close to randomly charged surfaces as compared with uniformly charged ones. The interaction pressure acting on the surfaces displays in general a highly non-monotonic behavior as a function of the inter-surface separation with a prominent regime of attraction at small to intermediate separations. This attraction is caused directly by the combined effects from charge disorder and strong coupling electrostatics of multivalent counterions, which dominate the surface-surface repulsion due to the (equal) mean charges on the two surfaces and the osmotic pressure of monovalent ions residing between them. These effects can be quite significant even with a small degree of surface charge disorder relative to the mean surface charge. The strong coupling, disorder-induced attraction is typically much stronger than the van der Waals interaction between the surfaces, especially within a range of several nanometers for the inter-surface separation, where such effects are predicted to be most pronounced.

摘要

我们研究了在携带淬火随机单极电荷且均值和方差相等的电介质表面之间,由强耦合库仑流体介导的有效相互作用,这两种情况分别是:库仑流体仅由可移动的多价抗衡离子组成,以及由包含多价和单价(盐)离子且与水性本体储层处于平衡状态的不对称离子混合物组成。我们分析了表面电荷无序、介电和盐镜像效应之间的相互作用,以及多价抗衡离子对这些离子分布和它们在表面之间介导的有效相互作用压力所产生的强静电耦合所带来的后果。在介电均匀的系统中,我们表明多价抗衡离子以一种奇异的、由无序诱导的势被吸引到表面,该势在接近表面时对数发散,产生一个奇异但可积的抗衡离子密度分布,其在表面呈现代数发散,指数取决于表面电荷(无序)方差。这种效应驱使系统趋向于一个热“无序”较低的状态,该状态可以用重整化温度来描述,从而表现出显著的抗脆弱性。在存在界面介电不连续性的情况下,表面处抗衡离子密度的奇异行为被消除,但与均匀带电表面相比,多价抗衡离子在随机带电表面附近的积累仍然要强得多。作用在表面上的相互作用压力通常表现出高度非单调的行为,作为表面间距离的函数,在小到中等距离处有一个显著的吸引区域。这种吸引直接由电荷无序和多价抗衡离子的强耦合静电的综合效应引起,它们主导了由于两个表面上(相等)的平均电荷以及它们之间的单价离子渗透压所产生的表面 - 表面排斥。即使相对于平均表面电荷而言表面电荷无序程度较小,这些效应也可能相当显著。强耦合、无序诱导的吸引力通常比表面之间的范德华相互作用要强得多,特别是在表面间距离为几纳米的范围内,预计这种效应最为明显。

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