Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
J Chem Phys. 2011 Sep 14;135(10):104104. doi: 10.1063/1.3632052.
In this report, a molecular Debye-Hückel theory for ionic fluids is developed. Starting from the macroscopic Maxwell equations for bulk systems, the dispersion relation leads to a generalized Debye-Hückel theory which is related to the dressed ion theory in the static case. Due to the multi-pole structure of dielectric function of ionic fluids, the electric potential around a single ion has a multi-Yukawa form. Given the dielectric function, the multi-Yukawa potential can be determined from our molecular Debye-Hückel theory, hence, the electrostatic contributions to thermodynamic properties of ionic fluids can be obtained. Applications to binary as well as multi-component primitive models of electrolyte solutions demonstrated the accuracy of our approach. More importantly, for electrolyte solution models with soft short-ranged interactions, it is shown that the traditional perturbation theory can be extended to ionic fluids successfully just as the perturbation theory has been successfully used for short-ranged systems.
在本报告中，我们开发了一种用于离子液体的分子德拜-休克尔理论。从大块系统的宏观麦克斯韦方程组出发，色散关系导致了广义的德拜-休克尔理论，该理论在静态情况下与包裹离子理论有关。由于离子液体介电函数的多极结构，单个离子周围的电势具有多-Yukawa 形式。给定介电函数，多-Yukawa 势可以从我们的分子德拜-休克尔理论中确定，因此可以得到离子液体热力学性质的静电贡献。二元和多组分原始电解质溶液模型的应用证明了我们方法的准确性。更重要的是，对于具有软短程相互作用的电解质溶液模型，表明传统的微扰理论可以成功地扩展到离子液体中，就像微扰理论已经成功地用于短程系统一样。
