Ben-Yaakov Dan, Andelman David, Harries Daniel, Podgornik Rudi
Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University, Ramat Aviv, Tel Aviv 69978, Israel.
J Phys Condens Matter. 2009 Oct 21;21(42):424106. doi: 10.1088/0953-8984/21/42/424106. Epub 2009 Sep 30.
The Poisson-Boltzmann mean-field description of ionic solutions has been successfully used in predicting charge distributions and interactions between charged macromolecules. While the electrostatic model of charged fluids, on which the Poisson-Boltzmann description rests, and its statistical mechanical consequences have been scrutinized in great detail, much less is understood about its probable shortcomings when dealing with various aspects of real physical, chemical and biological systems. These shortcomings are not only a consequence of the limitations of the mean-field approximation per se, but perhaps are primarily due to the fact that the purely Coulombic model Hamiltonian does not take into account various additional interactions that are not electrostatic in their origin. We explore several possible non-electrostatic contributions to the free energy of ions in confined aqueous solutions and investigate their ramifications and consequences on ionic profiles and interactions between charged surfaces and macromolecules.
泊松-玻尔兹曼离子溶液平均场描述已成功用于预测带电大分子之间的电荷分布和相互作用。虽然泊松-玻尔兹曼描述所基于的带电流体静电模型及其统计力学结果已得到详细审查，但对于其在处理实际物理、化学和生物系统的各个方面时可能存在的缺点，人们了解得要少得多。这些缺点不仅是平均场近似本身局限性的结果，而且可能主要是由于纯粹的库仑模型哈密顿量没有考虑到各种非静电起源的额外相互作用。我们探讨了受限水溶液中离子自由能的几种可能的非静电贡献，并研究了它们对离子分布以及带电表面与大分子之间相互作用的影响和后果。
