Mathieu Didier, Pipeau Yohann
CEA, DAM, Le Ripault, F-37260 Monts, France.
J Chem Theory Comput. 2010 Jul 13;6(7):2126-39. doi: 10.1021/ct100024r.
In view of identifying routine procedures to estimate formation enthalpies of ionic systems such as energetic salts or ionic liquids on the basis of density functional theory (DFT), various combinations of atom equivalent (AE) schemes, functionals, and basis sets are compared, using a specially designed training set to parametrize the models. After correction, none of the functionals considered proves significantly more reliable than B3LYP. A small but systematic improvement is noted as AE values are allowed to depend on the atomic environment. However, AE parameters fail to make up for basis set limitations, in constrast to previous observations for neutrals. Finally, a good trade-off between reliability and cost is obtained for ions using B3LYP/6-31++G** energies.
鉴于要确定基于密度泛函理论（DFT）估算高能盐或离子液体等离子体系生成焓的常规程序，我们比较了原子等效（AE）方案、泛函和基组的各种组合，并使用专门设计的训练集对模型进行参数化。经过校正后，所考虑的泛函中没有一个被证明比B3LYP更可靠。当允许AE值依赖于原子环境时，会注意到有一个虽小但系统的改进。然而，与之前对中性体系的观察结果相反，AE参数无法弥补基组的局限性。最后，使用B3LYP/6-31++G**能量对离子而言，在可靠性和成本之间实现了良好的权衡。
