Relativistic correlating basis sets for actinide atoms from 90Th to 103Lr
Relativistic correlating basis sets for actinide atoms from 90Th to 103Lr
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DOI：
10.1002/jcc.20537
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发表时间：
2007-12
影响因子：
3
通讯作者：
T. Noro;M. Sekiya;Y. Osanai;T. Koga;H. Matsuyama
中科院分区：
文献类型：
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作者：
T. Noro;M. Sekiya;Y. Osanai;T. Koga;H. Matsuyama
对于从90Th到103Lr的14个锕系原子，建立了用于描述5f， 6d和7s电子相关性的收缩高斯型函数集。由于6d轨道在分子环境中是重要的，尽管它们在某些锕系元素的基态中是空缺的，因此也制备了6d轨道的基集。采用分段收缩方案，既紧凑又高效。收缩系数和指数的确定是为了尽量减少由5fn−16d17s2结构引起的最低项与准确自然轨道的偏差。通过三阶Douglas - Kroll近似考虑了自旋自由相对论效应。为了验证目前的相关集，在90ThO分子的基态上进行了所有电子计算。计算得到的光谱常数与实验值吻合良好。©2007 Wiley期刊公司计算机学报，2007
For 14 actinide atoms from 90Th to 103Lr, contracted Gaussian‐type function sets are developed for the description of correlations of the 5f, 6d, and 7s electrons. Basis sets for the 6d orbitals are also prepared, since the orbitals are important in molecular environments despite their vacancy in the ground state of some actinides. A segmented contraction scheme is employed for the compactness and efficiency. Contraction coefficients and exponents are so determined as to minimize the deviation from accurate natural orbitals of the lowest term arising from the 5fn−16d17s2 configuration. The spin‐free relativistic effects are considered through the third‐order Douglas‐Kroll approximation. To test the present correlating sets, all‐electron calculations are performed on the ground state of 90ThO molecule. The calculated spectroscopic constants are in excellent agreement with experimental values. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007