Correlation consistent basis sets for explicitly correlated wavefunctions: Pseudopotential-based basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements
Correlation consistent basis sets for explicitly correlated wavefunctions: Pseudopotential-based basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements
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DOI：
10.1063/5.0070638
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发表时间：
2021-11-07
影响因子：
4.4
通讯作者：
Shaw, Robert A.
中科院分区：
文献类型：
--
作者：
Hill, J. Grant;Shaw, Robert A.
新的相关性一致的基组的第11组（Cu，Ag，Au）和12组（Zn，Cd，Hg）的元素已经开发专门用于显式相关的F12计算。这包括仅用于价（cc-pVnZ-PP-F12，n = D，T，Q）和外核-价（cc-pVnZ-PP-F12）相关性的轨道基组，沿着这两者都用附加的高角动量扩散函数增强。匹配辅助基组所需的密度拟合和分辨率的身份的方法，传统的和F12积分也进行了优化。所有的基组都将与小核相对论赝势结合使用[Figgen等人，311，227（2005）]。基组的准确性是通过基准计算确定的显式相关耦合簇理论水平的各种性质的原子和双原子分子。与传统的耦合簇计算相比，相对于基组的性质的收敛性得到了显着改善，cc-pVTZ-PP-F12结果接近完整基组极限的传统估计。收敛的模式也大大改善相比，从使用传统的相关一致的基组在F12计算中观察到的。(C)2021年作者。
New correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements have been developed specifically for use in explicitly correlated F12 calculations. This includes orbital basis sets for valence only (cc-pVnZ-PP-F12, n = D, T, Q) and outer core-valence (cc-pCVnZ-PP-F12) correlation, along with both of these augmented with additional high angular momentum diffuse functions. Matching auxiliary basis sets required for density fitting and resolution-of-the-identity approaches to conventional and F12 integrals have also been optimized. All of the basis sets are to be used in conjunction with small-core relativistic pseudopotentials [Figgen et al., Chem. Phys. 311, 227 (2005)]. The accuracy of the basis sets is determined through benchmark calculation at the explicitly correlated coupled-cluster level of theory for various properties of atoms and diatomic molecules. The convergence of the properties with respect to the basis set is dramatically improved compared to conventional coupled-cluster calculations, with cc-pVTZ-PP-F12 results close to conventional estimates of the complete basis set limit. The patterns of convergence are also greatly improved compared to those observed from the use of conventional correlation consistent basis sets in F12 calculations. (C) 2021 Author(s).