论文标题
部分可观测时空混沌系统的无模型预测
Performance of Localized-Orbital Coupled Cluster Approaches for the Conformational Energies of Longer n-alkane Chains
论文作者
论文摘要
我们报告了ACONFL的更新和增强（大烷烃的构象构象能量[Ehlert，s。; Grimme，S。; Hansen，A。J.Phys。Chem。A2022，126，3521-3535]）数据集。对于ACONF12（N-DODECANE）子集，我们报告了从MP2-F12/CC-PV {T，Q} Z-F12外推，[CCSD（F12*） - MP2-F12]/AUG-CCC-PVTZ-F12和A（T）Corrivenation的基础限制限制。 ccsd（t）/aug-cc-pv {d，t} z计算。然后，我们探讨了各种单一和复合局部轨道轨道CCSD（T）近似的性能，最终发现了基于基于0.008 kcal/mol MAD（平均绝对偏差）的基于MAR MAD（平均绝对偏差）的负担得起的LNO-CCSD（T）基于基于的MP2后校正。在与规范的MP2-F12/CBS外推同时，这分别用于重新评估n-Hexadecane和N-氨基烷的ACONF16和ACONF20子集。因此，获得了修订后的ACONFL集。然后，它用于评估不同局部轨道耦合群集方法的性能，例如在MOLPRO中实现的PNO-LCCSD（T），在ORCA中实现的DLPNO-CCSD（T1），以及在MRCC中实现的LNO-CCSD（T）在MRCC的各种精度设置中实现。与修订后的ACONFL参考数据相比，基于三层LNO-CCSD（T）基于基于0.02 kcal/mol的复合方案。当外推到完整的PNO空间限制时，DLPNO-CCSD（T1，TICK）和复合方法是所有针对十二烷构象异构体测试的局部耦合群集方法中的最佳选择。通过分散校正的基于DRPA的双重混合动力对于ACONFL套件的表现非常出色。虽然修订后的参考数据不会影响较不准确的方法的任何结论，但它们可能会为更准确的方法上下订购，其错误统计信息与参考数据集之间的差异相同。
We report an update and enhancement of the ACONFL (conformer energies of large alkanes [Ehlert, S.; Grimme, S.; Hansen, A. J. Phys. Chem. A 2022, 126, 3521-3535]) dataset. For the ACONF12 (n-dodecane) subset, we report basis set limit canonical CCSD(T) reference data obtained from MP2-F12/cc-pV{T,Q}Z-F12 extrapolation, [CCSD(F12*)-MP2-F12]/aug-cc-pVTZ-F12, and a (T) correction from conventional CCSD(T)/aug-cc-pV{D,T}Z calculations. Then we explored the performance of a variety of single and composite localized-orbital CCSD(T) approximations, ultimately finding an affordable LNO-CCSD(T)-based post-MP2 correction that agrees to 0.008 kcal/mol MAD (mean absolute deviation) with the revised canonical reference data. In tandem with canonical MP2-F12/CBS extrapolation, this was then used to re-evaluate the ACONF16 and ACONF20 subsets for n-hexadecane and n-icosane, respectively. A revised ACONFL set was thus obtained. It was then used to assess the performance of different localized-orbital coupled cluster approaches, such as PNO-LCCSD(T) as implemented in MOLPRO, DLPNO-CCSD (T1) as implemented in ORCA, and LNO-CCSD(T) as implemented in MRCC, at their various accuracy settings. A three-tier LNO-CCSD(T)-based composite scheme disagrees by only 0.02 kcal/mol from the revised ACONFL reference data. When extrapolated to the complete PNO space limit, DLPNO-CCSD(T1, Tight) and a composite method are the best picks among all the localized coupled cluster methods tested for the dodecane conformers. Dispersion-corrected dRPA-based double hybrids perform remarkably well for the ACONFL set. While the revised reference data do not affect any conclusions on the less accurate methods, they may upend orderings for more accurate methods with error statistics on the same order as the difference between reference datasets.
