Asia Pacific Center for Theoretical Physics, Pohang, Gyeongbuk-do, Korea.
PLoS One. 2013 Aug 5;8(8):e69436. doi: 10.1371/journal.pone.0069436. Print 2013.
The repulsive interaction between oppositely charged macroions is investigated using Grand Canonical Monte Carlo simulations of an unrestricted primitive model, including the effect of inhomogeneous surface charge and its density, the depth of surface charge, the cation size, and the dielectric permittivity of solvent and macroions, and their contrast. The origin of the repulsion is a combination of osmotic pressure and ionic screening resulting from excess salt between the macroions. The excess charge over-reduces the electrostatic attraction between macroions and raises the entropic repulsion. The magnitude of the repulsion increases when the dielectric constant of the solvent is lowered (below that of water) and/or the surface charge density is increased, in good agreement with experiment. Smaller size of surface charge and the cation, their discreteness and mobility are other factors that enhance the repulsion and charge inversion phenomenons.
使用非限制原始模型的巨正则蒙特卡罗模拟研究带相反电荷的大离子之间的排斥相互作用,包括不均匀表面电荷及其密度、表面电荷深度、阳离子大小、溶剂和大离子的介电常数及其对比的影响。排斥的起源是大离子之间过剩盐引起的渗透压和离子屏蔽的组合。过剩电荷过度减少了大离子之间的静电吸引力,并增加了熵排斥。当溶剂的介电常数降低(低于水)和/或表面电荷密度增加时,排斥力的大小会增加,这与实验结果一致。较小的表面电荷和阳离子尺寸、离散性和迁移率是增强排斥和电荷反转现象的其他因素。