论文标题
基于规范和DLPNO的复合波函数方法针对大型和化学多样的训练集进行了参数。 2。相关一致的基集，核心价相关和F12替代方案
Canonical and DLPNO-based composite wavefunction methods parametrized against large and chemically diverse training sets. 2. Correlation consistent basis sets, core-valence correlation, and F12 alternatives
论文作者
论文摘要
Semidalas和Martin最近报道了基于可用于元件H至RN的G4-型CWFT方法的波函数复合方法（CWFT）的层次结构[J. [J.化学理论。计算。 2020，16，4238]。我们通过在二阶软体动物式校正中考虑内部壳相关能量并替换上述纸中使用的weigend-ahlrichs def2-mzvpp（d），并取代上述纸张中使用的weigend-ahlrichs def2-mzvpp（d），以完整的基础设置额外汇总，从增强的相关性核心核心三重核），aug-zeta，aug-ccwc（aug-ccc-ccwc cantrence and-aug-cccwc（aug-ccc-ccwc and），我们扩展了这种层次结构。 QUADRUPLE-ZETA，AUG-CC-PWCVQZ（-PP），基集，从而创建CC-G4-类型方法。对于大型且化学多样的GMTKN55基准套件，它们代表了实质性的进一步改进，并使WTMAD2（加权平均绝对偏差）降至1 kcal/mol以下。有趣的是，狮子在改善中的份额来自更好地捕获价相关性。核心价相关的包含几乎不太重要。这些强大的相关性一致的CWFT方法仅使用一个或几个拟合的参数将CCSD（t）完整的基限使用。特别是DLPNO变体（例如CC-G4-T-DLPNO）适用于相当大的分子，以适度的计算成本，以及使用MP2-F12/CC-PVTZ-F12的不同变体用于MP2分量。
A hierarchy of wavefunction composite methods (cWFT), based on G4- type cWFT methods available for elements H through Rn, was recently reported by Semidalas and Martin [J. Chem. Theor. Comput. 2020, 16, 4238]. We extend this hierarchy by considering the inner-shell correlation energy in the second-order Moller-Plesset correction and replacing the Weigend-Ahlrichs def2-mZVPP(D) basis sets used in the aforementioned paper with complete basis set extrapolation from augmented correlation consistent core-valence triple-zeta, aug-cc-pwCVTZ(-PP), and quadruple-zeta, aug-cc-pwCVQZ(-PP), basis sets, thus creating cc-G4- type methods. For the large and chemically diverse GMTKN55 benchmark suite, they represent a substantial further improvement and bring WTMAD2 (weighted mean absolute deviation) down below 1 kcal/mol. Intriguingly, the lion's share of the improvement comes from better capture of valence correlation; the inclusion of core-valence correlation is almost an order of magnitude less important. These robust correlation consistent cWFT methods approach the CCSD(T) complete basis limit with just one or a few fitted parameters. Particularly the DLPNO variants such as cc-G4-T-DLPNO are applicable to fairly large molecules at modest computational cost, as is (for a reduced range of elements) a different variant using MP2-F12/cc-pVTZ-F12 for the MP2 component.
