关于偶极矩的计算--关于基组选择和理论水平的建议
On the Computation of Dipole Moments: A Recommendation on the Choice of the Basis Set and the Level of Theory
摘要：
结合实验数据，理论上预测的偶极矩为化学和物理科学的不同分支提供了一个有价值的工具。由于理论和基组水平的多样性，必须仔细选择可靠的组合才能实现准确的预测。在最近的出版物（arXiv：1709.05075 [physics.chem-ph]）中，Hait和Head-Gordon在这方面迈出了第一步，提供了适合这些目的的最佳密度泛函的建议。然而，没有进行广泛的研究，以提供建议的基础设置的选择。在这里，我们通过评估38个通用基组的单到三重zeta质量的性能，当与九个不同层次的理论相结合时，在计算偶极矩时，对这个问题进行了一些说明。计算是在一个数据集上进行的，该数据集包含114个含有第二和第三行元素的小分子。我们的分析基于正则化均方根误差（正则化RMSE），因为该程序确保了离子物质的相对误差和具有小偶极矩值的物质的绝对误差。我们的研究结果表明，精度和计算效率之间的最佳折衷是通过使用增广的双zeta质量基集（即aug-pc-1，aug-pcseg-1，aug-cc-pVDZ）与混合泛函（例如wB 97 X-V，SOGGA 11-X）一起执行计算来实现的。增强的三重zeta基组可以提高计算的准确性，但引入这样的基组的计算成本是相当大的相比，提供的小的改进。这些发现也突出了至关重要的作用，增强的基础设置与扩散功能的氢原子和非氢原子在计算的偶极矩。
英文摘要：
Together with experimental data, theoretically predicted dipole moments represent a valuable tool for different branches in the chemical and physical sciences. With the diversity of levels of theory and basis sets available, a reliable combination must be carefully chosen in order to achieve accurate predictions. In a recent publication (arXiv:1709.05075 [physics.chem-ph]), Hait and Head-Gordon took a first step in this regard by providing recommendations on the best density functionals suitable for these purposes. However, no extensive study has been performed to provide recommendations on the basis set choice. Here, we shed some light into this matter by evaluating the performance of 38 general-purpose basis sets of single up to triple zeta-quality, when coupled with nine different levels of theory, in the computation of dipole moments. The calculations were performed on a data set with 114 small molecules containing second- and third-row elements. We based our analysis in regularised root mean square errors (regularised RMSE) as this procedure ensures relative errors for ionic species and absolute errors for species with small dipole moment values. Our results indicate that the best compromise between accuracy and computational efficiency is achieved by performing the computations with an augmented double zeta-quality basis set (i.e. aug-pc-1, aug-pcseg-1, aug-cc-pVDZ) together with a hybrid functional (e.g. wB97X-V, SOGGA11-X). Augmented triple-zeta basis sets could enhance the accuracy of the computations, but the computational cost of introducing such a basis set is substantial compared with the small improvement provided. These findings also highlight the crucial role that augmentation of the basis set with diffuse functions on both hydrogen and non-hydrogen atoms plays in the computation of dipole moments.
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