论文标题
强限制方案中的电解质:表面电荷调制,渗透平衡和电击
Electrolytes in regimes of strong confinements: surface charge modulations, osmotic equilibrium and electroneutrality
论文作者
论文摘要
在目前的工作中,我们研究了一个限制在具有非公开电荷域的平面表面之间的电解质溶液,该域已连接到散装离子储层。通过改进的蒙特卡洛(MC)模拟方法研究了该系统,适用于在有调制的表面电荷分布的情况下模拟电解质。我们还以经典的Debye-Hückel近似精神采用线性方法,该方法使人们可以为平均电势,离子剖面,有效的表面相互作用和隔离墙之间的净离子电荷获得明确的表达。重点放在强限的电解质的极限中,在这种情况下,可能无法满足地面间空间中的局部电压。为了访问这种缺乏局部电荷中性的影响对与电荷域之间离子诱导的表面之间的相互作用的影响,我们考虑了两个限制电解质的两个不同的模型系统:一种明确考虑盐储层的盐储存液,并通过}与固定构成固定浓度的稳定性平衡,以及一个等式的一个等式,以及一个等式的一个等式,以及一个等式的一个方程。被隐式考虑。虽然在前一种情况下,渗透离子交换可能会导致无易变的净电荷,但在后一种模型电荷中,通过在带电的接口中出现隐式唐南电位,从而实现了中立性。在所有粒子分离上都观察到了离子诱导的模型系统中离子诱导的表面相互作用的强烈依赖性。这些发现强烈表明,在不同情况下选择应有的谨慎,以描述限制在带电表面之间的电解质中的离子交换,即使在不存在单极(非净净电荷)表面贡献的情况下。
In the present work, we study an electrolyte solution confined between planar surfaces with nonopatterned charged domains, which has been connected to a bulk ionic reservoir. The system is investigated through an improved Monte Carlo (MC) simulation method, suitable for simulation of electrolytes in the presence of modulated surface charge distributions. We also employ a linear approach in the spirit of the classical Debye-Hückel approximation, which allows one to obtain explicit expressions for the averaged potentials, ionic profiles, effective surface interactions and the net ionic charge confined between the walls. Emphasis is placed in the limit of strongly confined electrolytes, in which case local electroneutrality in the inter-surface space might not be fulfilled. In order to access the effects of such lack of local charge neutrality on the ionic-induced interactions between surfaces with modulated charge domains, we consider two distinct model systems for the confined electrolyte: one in which a salt reservoir is explicitly taken into account {\it via} the osmotic equilibrium with an electrolyte of fixed bulk concentration, and a second one in which the equilibrium with a charge neutral ionic reservoir is implicitly considered. While in the former case the osmotic ionic exchange might lead to non-vanishing net charges, in the latter model charge neutrality is enforced through the appearance of an implicit Donnan potential across the charged interfaces. A strong dependence of the ionic-induced surface interactions in the employed model system is observed at all particle separations. These findings strongly suggest that due care is to be taken while choosing among different scenarios to describe the ionic exchanging in electrolytes confined between charged surfaces, even in cases when the monopole (non zero net charge) surface contributions are absent.