Mohanty U, Ninham B W, Oppenheim I
Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02167, USA.
Proc Natl Acad Sci U S A. 1996 Apr 30;93(9):4342-4. doi: 10.1073/pnas.93.9.4342.
The phenomenon of Manning-Oosawa counterion condensation is given an explicit statistical mechanical and qualitative basis via a dressed polyelectrolyte formalism in connection with the topology of the electrostatic free-energy surface and is derived explicitly in terms of the adsorption excess of ions about the polyion via the nonlinear Poisson-Boltzmann equation. The approach is closely analogous to the theory of ion binding in micelles. Our results not only elucidate a Poisson-Boltzmann analysis, which shows that a fraction of the counterions lie within a finite volume around the polyion even if the volume of the system tends towards infinity, but also provide a direct link between Manning's theta-the number of condensed counterions for each polyion site-and a statistical thermodynamic quantity, namely, the adsorption excess per monomer.
通过与静电自由能表面拓扑结构相关的着装聚电解质形式，给出了曼宁 - 大泽反离子凝聚现象明确的统计力学和定性基础，并通过非线性泊松 - 玻尔兹曼方程，根据围绕聚离子的离子吸附过量明确推导得出。该方法与胶束中离子结合理论极为相似。我们的结果不仅阐明了泊松 - 玻尔兹曼分析，该分析表明即使系统体积趋于无穷大，仍有一部分反离子位于聚离子周围的有限体积内，而且还在曼宁的θ（每个聚离子位点凝聚的反离子数）与一个统计热力学量（即每个单体的吸附过量）之间建立了直接联系。
