AI 中文总结
该研究基于泊松-玻尔兹曼理论，揭示受限电解质中局部电中性的有限尺寸偏差遵循拓扑层级，发现带电纳米颗粒存在内部受限电荷反转，为评估非泊松-玻尔兹曼框架下的拓扑效应提供基准。
AI 中文摘要
拓扑决定了受限电解质中局部电中性的有限尺寸违反。在泊松-玻尔兹曼（Poisson-Boltzmann）理论框架内，我们证明这种拓扑控制会在球形、圆柱形和平面受限体系中产生普适的偏差层级。我们通过电中性偏差比来量化该效应，该比值可捕捉对应狭缝、圆柱形和球形腔三种拓扑类别中，与致密性及边界多重性相关的全局静电约束。尽管在腔尺寸趋于无穷大的极限下，局部电中性会渐近恢复，但有限尺寸偏差遵循稳健的拓扑层级：球形腔中最强，圆柱形受限体系中较弱，平面狭缝中最弱。这些结果证明，拓扑是受限诱导电荷重新分布的组织原则，而局部电中性的违反是控制过充电、电荷反转及长程电荷关联的通用静电约束。更根本的是，它们表明改变拓扑结构会修改全局静电约束，而无需改变局部泊松-玻尔兹曼方程。作为点离子模型中非线性受限的反直觉表现，我们报道了带电空心圆柱形和球形纳米颗粒中存在内部受限电荷反转（ICCR）。由于物理上自洽的更通用电解质理论必须在适当极限下恢复泊松-玻尔兹曼描述，本研究结果为评估泊松-玻尔兹曼描述之外的拓扑效应建立了基准。
英文摘要
Topology governs finite-size violations of local electroneutrality in confined electrolytes. Within Poisson-Boltzmann theory, we show that this topological control gives rise to a universal hierarchy of deviations in spherical, cylindrical, and planar confinement. We quantify this effect through an electroneutrality deviation ratio that captures the global electrostatic constraints associated with compactness and boundary multiplicity in the three topological classes corresponding to slit, cylindrical, and spherical cavities. Although local electroneutrality is asymptotically restored in the limit of infinite cavity size, finite-size deviations follow a robust topological hierarchy, being strongest in spherical cavities, weaker in cylindrical confinement, and weakest in planar slits. These results prove that topology is the organizing principle underlying confinement-induced charge redistribution and that violations of local electroneutrality constitute a general electrostatic constraint governing overcharging, charge reversal, and long-range charge correlations. More fundamentally, they demonstrate that changing the topology modifies the global electrostatic constraints without altering the local Poisson-Boltzmann equations. As a counterintuitive manifestation of nonlinear confinement in a point-ion model, we report the existence of inside confinement charge reversal (ICCR) in charged hollow cylindrical and spherical nanoparticles. Since physically consistent, more general electrolyte theories must recover the Poisson-Boltzmann description in the appropriate limiting case, the present results establish a benchmark against which topological effects should be assessed beyond the Poisson-Boltzmann description.
Comments14 pages, 5 figures, 2 appendix
