Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements
Gaussian basis sets for use in correlated molecular calculations. XI. Pseudopotential-based and all-electron relativistic basis sets for alkali metal (K-Fr) and alkaline earth (Ca-Ra) elements
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DOI：
10.1063/1.5010587
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发表时间：
2017-12-28
影响因子：
4.4
通讯作者：
Peterson, Kirk A.
中科院分区：
文献类型：
--
作者：
Hill, J. Grant;Peterson, Kirk A.
基于伪能力（PP）哈密顿量的新相关性一致的基集已从已故碱（K-FR）和碱（CA-RA）金属的双向五重和Zeta质量开发。这些都伴随着新的全电子基础基集，这些基于双向四倍 - Zeta质量，这些质量已与Douglas-Kroll-Hess（DKH）和精确的2-Compent（X2C）标量相对论Hamiltonians一起使用。价值相关性（MS），CC-PVNZ-PP和CC-PVNZ-（DK，DK3/X2C）的集合，除了外部核心相关[Valence +（M-1）SP]，CC-P（W）报道了CVNZ-PP和CC-PWCVNZ-（DK，DK3/X2C）。 PPP集已开发用于小核PPS [I。 S. Lim等人，J。Chem。物理。 122，104103（2005）和I. S. Lim等人，J。Chem。物理。 124，034107（2006）]，而全电子设置的设置为4s和5s元素使用二阶DKH Hamiltonians，以及6s和7s的第三阶DKH。基集的准确性是通过在原子和分子特性的耦合群集理论水平上的基准计算来评估的。毫不奇怪，发现外部核心相关对于精确计算包含这些元素的硅藻分子的热力学和光谱特性至关重要。 （c）2017年作者。
New correlation consistent basis sets based on pseudopotential (PP) Hamiltonians have been developed from double-to quintuple-zeta quality for the late alkali (K-Fr) and alkaline earth (Ca-Ra) metals. These are accompanied by new all-electron basis sets of double-to quadruple-zeta quality that have been contracted for use with both Douglas-Kroll-Hess (DKH) and eXact 2-Component (X2C) scalar relativistic Hamiltonians. Sets for valence correlation (ms), cc-pVnZ-PP and cc-pVnZ-(DK,DK3/X2C), in addition to outer-core correlation [valence + (m-1)sp], cc-p(w)CVnZ-PP and cc-pwCVnZ-(DK,DK3/X2C), are reported. The-PP sets have been developed for use with small-core PPs [I. S. Lim et al., J. Chem. Phys. 122, 104103 (2005) and I. S. Lim et al., J. Chem. Phys. 124, 034107 (2006)], while the all-electron sets utilized second-order DKH Hamiltonians for 4s and 5s elements and third-order DKH for 6s and 7s. The accuracy of the basis sets is assessed through benchmark calculations at the coupled-cluster level of theory for both atomic and molecular properties. Not surprisingly , it is found that outer-core correlation is vital for accurate calculation of the thermodynamic and spectroscopic properties of diatomic molecules containing these elements. (C) 2017 Author(s).