小分子体系高阶多极矩与极化率张量的基准测试
Benchmarking higher-ranking multipoles and polarizability tensors for small molecular systems
AI总结：
本工作为73个小分子提供CCSD(T)参考值，系统评估多种量子化学方法计算偶极、四极矩及极化率的性能，发现B97-3-AC最优，并指出基组选择要点。
AI中文摘要：
分子性质决定了分子之间或与外部场的相互作用方式。准确的分子性质对于构建分子间相互作用模型至关重要，而要实现高精度，我们需要超越最低阶（偶极）项。本工作为73个小的非自旋极化分子提供了CCSD(T)参考值，涵盖分子偶极矩和四极矩，以及偶极-偶极和四极-四极极化率。利用这些结果，我们对使用HF、MP2、CCSD以及多种密度泛函方法计算的分子性质进行了全面的性能分析。此外，我们详细研究了需要何种水平的基组才能同时准确描述数据集中的所有性质。对于所有四种性质，表现最佳的密度泛函是渐近校正的杂化GGA B97-3-AC，紧随其后的是PBE0-AC。令人惊讶的是，现代meta-GGA和范围分离泛函表现不稳定，在四极性质上存在较大误差。这些结果对分子间相互作用的方法（如基于密度泛函理论的对称适应微扰理论）或机器学习数据集中性质与相互作用的质量具有直接影响。最后，对于DFT方法，Jensen aug-pcseg-2基组是比更成熟基组计算上更高效的替代方案，但为了生成相关参考值，第三行元素受益于芯极化，而双增强对于四极-四极极化率是严格必需的。
英文摘要：
Molecular properties govern how molecules interact with one another or external fields. Accurate molecular properties are essential for constructing intermolecular interaction models, and to achieve high accuracy we need to go beyond leading-order (dipolar) terms. This work presents CCSD(T) references for 73 small non-spin-polarized molecules for molecular dipole and quadrupole moments, and dipole-dipole and quadrupole-quadrupole polarizabilities. Using these results, we provide a holistic performance analysis of molecular properties computed with HF, MP2, CCSD, and a wide range of density-functional methods. Additionally, we investigate in detail what levels of basis sets are required to simultaneously describe all properties in the data set. The best-performing density functionals for all four properties are the asymptotically cor- rected hybrid GGAs B97-3-AC, closely followed by PBE0-AC. Surprisingly, modern meta- GGAs and range-separated functionals perform inconsistently, with large errors in the quadrupo- lar properties. These results have direct implications for methods for intermolecular interac- tions, such as symmetry-adapted perturbation theory based on density functional theory, or for the quality of properties and interactions in machine-learning datasets. Finally, for DFT methods, the Jensen aug-pcseg-2 basis set is a computationally efficient alternative to more established basis sets, but for generating correlated references, third-row elements benefit from core polarization, and double augmentation is strictly necessary for quadrupole-quadrupole polarizabilities.
