Laboratory of Atmospheric Physico-Chemistry, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei, Anhui, 230031, China.
J Comput Chem. 2014 Jan 15;35(2):159-65. doi: 10.1002/jcc.23477. Epub 2013 Oct 31.
Cl(-)(H2O)n (n = 1-4) clusters were investigated using a basin-hopping (BH) algorithm coupled with density functional theory (DFT). Structures, energetics, thermodynamics, vertical detachment energies, and vibrational frequencies were obtained from high-level ab initio calculations. Through comparisons with previous theoretical and experimental data, it was demonstrated that the combination of the BH method and DFT could accurately predict the global and local minima of Cl(-)(H2O)n (n = 1-4). Additionally, to optimize larger Cl(-)(H2O)n (n > 4) clusters, several popular density functionals as well as DF-LMP2 (Schütz et al., J. Chem. Phys. 2004, 121, 737) (second-order Møller-Plesset perturbation theory using local and density fitting approximations) were tested with appropriate basis sets through comparisons with MP2 optimized results. DF-LMP2 will be used in future studies because its overall performance in describing the relative binding energies and the geometrical parameters of Cl(-)(H2O)n (n = 1-4) was outstanding in this study.
采用 basin-hopping（BH）算法结合密度泛函理论（DFT）研究了 Cl(-)(H2O)n（n=1-4）团簇。通过高精度从头算计算得到了结构、能量、热力学、垂直离解能和振动频率。通过与先前的理论和实验数据进行比较，证明了 BH 方法和 DFT 的结合可以准确预测 Cl(-)(H2O)n（n=1-4）的全局和局部最小值。此外，为了优化更大的 Cl(-)(H2O)n（n>4）团簇，通过与 MP2 优化结果的比较，测试了几种流行的密度泛函和 DF-LMP2（Schütz 等人，J. Chem. Phys. 2004, 121, 737）（使用局部和密度拟合近似的二级 Møller-Plesset 微扰理论）与适当的基组相结合。由于在本研究中，DF-LMP2 在描述 Cl(-)(H2O)n（n=1-4）的相对结合能和几何参数方面的整体性能非常出色，因此将在未来的研究中使用它。
