Accurate relativistic Gaussian basis sets determined by the third-order Douglas-Kroll approximation with a finite-nucleus model
Accurate relativistic Gaussian basis sets determined by the third-order Douglas-Kroll approximation with a finite-nucleus model
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DOI：
10.1063/1.1470496
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发表时间：
2002-05-15
影响因子：
4.4
通讯作者：
Hirao, K
中科院分区：
文献类型：
--
作者：
Nakajima, T;Hirao, K
在有限核模型下，建立了从H（Z=1）到Lr（Z=103）的103个元素的高精度相对论高斯基组。目前的GTO集增加了相对论基组与点电荷模型中提出的第一篇论文，这一系列。采用相对论三阶Douglas-Kroll方法，以原子自洽场（SCF）能量最小为目标，优化基组的轨道指数。基组的设计具有相同的质量，并适合于纳入相对论效应。通过使用SCF和具有微扰三重态的单双耦合簇模型[CCSD（T）]对原型分子金二聚体进行计算，测试了本基组的性能。计算了Au-2基态的几个光谱常数。在基组叠加误差（BSSE）校正的CCSD（T）水平下，与实验的偏差为Δ R（e）=0.018埃，Δ ω（e）=-3 cm（-1），Δ D（e）=-0.17 eV。有限尺寸核效应使R-e、Ω（e）和D-e分别减小0.004平行于、1 cm（-1）和0.05 eV。应用结果表明，本文提出的有限核相对论高斯型轨道基组是准确可靠的。(C)2002年美国物理学会。
Highly accurate relativistic Gaussian basis sets with a finite-nucleus model are developed for the 103 elements from H (Z=1) to Lr (Z=103). The present GTO sets augment the relativistic basis sets with a point-charge model proposed in the first paper of this series. The relativistic third-order Douglas-Kroll approach is adopted in optimizing the orbital exponents of a basis set by minimizing the atomic self-consistent field (SCF) energy. The basis sets are designed to have equal quality and to be appropriate for the incorporation of relativistic effects. The performance of the present basis sets is tested by calculations on a prototypical molecule, gold dimer using SCF and the singles and doubles coupled-cluster model with perturbative triples [CCSD(T)]. Several spectroscopic constants are calculated for the ground state of Au-2. At the basis set superposition error (BSSE) corrected CCSD(T) level, the deviation from experiment is DeltaR(e)=0.018 Angstrom, Deltaomega(e)=-3 cm(-1), and DeltaD(e)=-0.17 eV. The finite-size nucleus effect makes R-e, omega(e), and D-e smaller by 0.004 parallel to, 1 cm(-1), and 0.05 eV, respectively. The application shows that the present relativistic Gaussian-type orbitals (GTO) basis sets with a finite-nucleus model are accurate and reliable. (C) 2002 American Institute of Physics.