密度泛函理论在带电半透膜性质研究中的应用.pdf

A044 密度泛函理论在带电半透膜性质研究中的应用* 于养信**，王淑梅，高光华 (清华大学化学工程系，北京 100084) 摘 要 本文建立了带电半透膜的简单模型，除静电作用外，膜与其附近的离子之间的色散能用 方阱势能函数来表示。我们用密度泛函理论研究了膜面电荷密度和离子直径比对各离子在半透膜 附近密度分布的影响，其离子密度分布与Monte Carlo 模拟数据符合得很好。密度泛函理论预测 结果表明，膜面电荷密度越大，被吸附到膜中的离子越多，膜面电荷对大离子密度分布的影响要 大于小离子。 关键词 密度泛函理论 半透膜 离子分布 中图分类号 TQ013 文献标识码 A APPLICATION OF DENSITY FUNCTIONAL THEORY ON THE STUDY OF PROPERTIES OF CHARGED SEMIPERMEABLE MEMBRANE YU Yangxin, WANG Shumei and GAO Guanghua (Department of Chemical Engineering, Tsinghua University, Beijing 100084) Abstract A simple model is considered for charged semipermeable membrane. In addition to the electrostatic potential, the square-well potential is used to describe the interactions between the membrane and the surrouding ions. The density functional theory is applied to investigating the effects of the membrane surface charge density and the ratio of ionic diameters on the ionic density profiles near the membrane. The predicted ionic density profiles are in excellent agreement with the Monte Carlo simulation data. The results predicted from the density functional theory show that a quite large number of ions are absorbed into the membrane at high charge density, and the membrane surface charges have a greater effect on macroions than that on microions. Keywords density functional theory, semipermeable membrane, ionic distribution 引 言 由半透膜隔开的两种电解质溶液的物理性质在细胞生物学、胶体化学和化学工程中有着重要的意义。 一般在电解质水溶液中膜研究的表面会带一些净电荷，这样在流体-膜界面处会有一系列由界面和电化学共 同作用的现象出现。传统的Poisson-Boltzmann方程仅适用于 1:1 价电解质在低浓情况下的电荷分布。以往 的理论研究[1, 2]，大部分都假