Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo, Kyoto 615-8510, Japan.
J Chem Phys. 2012 Jul 14;137(2):024106. doi: 10.1063/1.4733393.
Integral equation theory for molecular liquids is one of the powerful frameworks to evaluate solvation free energy (SFE). Different from molecular simulation methods, the theory computes SFE in an analytical manner. In particular, the correction method proposed by Kovalenko and Hirata [Chem. Phys. Lett. 290, 237 (1998); and J. Chem. Phys. 113, 2793 (2000)] is quite efficient in the accurate evaluation of SFE. However, the application has been limited to aqueous solution systems. In the present study, an improved method is proposed that is applicable to a wide range of solution systems. The SFE of a variety of solute molecules in chloroform and benzene solvents is evaluated. A key is the adequate treatment of excluded volume in SFE calculation. By utilizing the information of chemical bonds in the solvent molecule, the accurate computation of SFE is achieved.
分子液体的积分方程理论是评估溶剂化自由能（SFE）的强大框架之一。与分子模拟方法不同，该理论以分析方式计算 SFE。特别是，Kovalenko 和 Hirata 提出的修正方法[Chem. Phys. Lett. 290, 237 (1998); 和 J. Chem. Phys. 113, 2793 (2000)]在准确评估 SFE 方面非常有效。然而，该应用仅限于水溶剂体系。在本研究中，提出了一种改进的方法，该方法适用于广泛的溶液体系。评估了各种溶质分子在氯仿和苯溶剂中的 SFE。关键是在 SFE 计算中对排除体积进行适当处理。通过利用溶剂分子中化学键的信息，可以实现 SFE 的精确计算。
