Yu Yang-Xin, Wu Jianzhong, Gao Guang-Hua
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
J Chem Phys. 2004 Apr 15;120(15):7223-33. doi: 10.1063/1.1676121.
A density-functional theory is proposed to describe the density profiles of small ions around an isolated colloidal particle in the framework of the restricted primitive model where the small ions have uniform size and the solvent is represented by a dielectric continuum. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for the hard-sphere repulsion and a quadratic functional Taylor expansion for the electrostatic interactions. The theoretical predictions are in good agreement with the results from Monte Carlo simulations and from previous investigations using integral-equation theory for the ionic density profiles and the zeta potentials of spherical particles at a variety of solution conditions. Like the integral-equation approaches, the density-functional theory is able to capture the oscillatory density profiles of small ions and the charge inversion (overcharging) phenomena for particles with elevated charge density. In particular, our density-functional theory predicts the formation of a second counterion layer near the surface of highly charged spherical particle. Conversely, the nonlinear Poisson-Boltzmann theory and its variations are unable to represent the oscillatory behavior of small ion distributions and charge inversion. Finally, our density-functional theory predicts charge inversion even in a 1:1 electrolyte solution as long as the salt concentration is sufficiently high.
提出了一种密度泛函理论,用于在受限原始模型框架内描述孤立胶体颗粒周围小离子的密度分布,其中小离子具有均匀尺寸,溶剂由介电连续体表示。过量亥姆霍兹能量泛函由用于硬球排斥的修正基本度量理论和用于静电相互作用的二次泛函泰勒展开推导得出。理论预测与蒙特卡罗模拟结果以及先前使用积分方程理论对各种溶液条件下球形颗粒的离子密度分布和zeta电位的研究结果高度吻合。与积分方程方法一样,密度泛函理论能够捕捉小离子的振荡密度分布以及高电荷密度颗粒的电荷反转(过充电)现象。特别是,我们的密度泛函理论预测在高电荷球形颗粒表面附近会形成第二个反离子层。相反,非线性泊松-玻尔兹曼理论及其变体无法表示小离子分布的振荡行为和电荷反转。最后,我们的密度泛函理论预测,只要盐浓度足够高,即使在1:1电解质溶液中也会发生电荷反转。
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