Institute of New Energy Material Chemistry, Tianjin Key Laboratory of Metal- and Molecule-Based Material Chemistry, Nankai University, Tianjin 300071, China.
J Phys Chem A. 2013 Jan 10;117(1):219-27. doi: 10.1021/jp3105908. Epub 2012 Dec 19.
The anisotropic ionic polarizabilities of two data sets of 216 cations (158 in training set and 58 in test set) and 80 anions (64 in training set and 16 in test set), which can be the components of ionic liquids (ILs), are fitted with Thole model against ab initio calculations. The isotropic atomic polarizabilities of H, B, C, N, O, F, S, Cl, P, and Br, are fitted for cations and anions, respectively, with two different smearing functions. The ab initio anisotropic ionic polarizabilities are well fitted by Thole model with a universal set of isotropic atomic polarizabilities, which are independent of their individual chemical environment. The current study also demonstrates the good transferability of Thole model to ions of different substituents, different side chain length, and different conformations.
我们采用 Thole 模型对来自两个数据集的 216 个阳离子（158 个在训练集中，58 个在测试集中）和 80 个阴离子（64 个在训练集中，16 个在测试集中）的各向异性离子极化率进行了拟合，这些阳离子和阴离子都是离子液体（ILs）的组成部分。我们还分别使用两种不同的平滑函数，对 H、B、C、N、O、F、S、Cl、P 和 Br 的各向同性原子极化率进行了拟合。Thole 模型可以很好地拟合从头算得到的各向异性离子极化率，而且模型中所用到的各向同性原子极化率是通用的，与离子所处的化学环境无关。本研究还证明了 Thole 模型对具有不同取代基、不同侧链长度和不同构象的离子具有良好的可转移性。
