规范和DLPNO为基础的复合波函数方法参数化对大型和化学不同的训练集。2.相关性一致基组、核价相关性和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
摘要：
基于可用于元素H至Rn的G4型cWFT方法的波函数复合方法（cWFT）的层级最近由Semidalas和Martin报道[J. Chem. Theor. Comput. 2020，16，4238]。我们通过考虑二阶Moller-Plesset校正中的内壳层相关能并将上述论文中使用的Weigend-Ahlrichs def 2-mZVPP（D）基组替换为从增强相关一致的核价三重zeta，aug-cc-mZVTZ（-PP）和四重zeta，aug-cc-mZVQZ（-PP）基组进行的完整基组外推，扩展了这一层次，从而创建了cc-G4型方法。对于大型和化学多样的GMTKN 55基准套件，它们代表了实质性的进一步改进，并使WTMAD 2（加权平均绝对偏差）降至1 kcal/mol以下。有趣的是，改进的最大部分来自更好地捕获价相关性;包括核心价相关性几乎是一个数量级不那么重要。这些稳健的相关一致cWFT方法仅用一个或几个拟合参数就接近CCSD（T）完全基极限。特别地，DLPNO变体如cc-G4-T-DLPNO以适度的计算成本适用于相当大的分子，如（对于减少的元素范围）使用MP2-F12/cc-pVTZ-F12用于MP2组分的不同变体。
英文摘要：
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.
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