Contribution to the electron distribution analysis. I. Shell structure of atoms
Contribution to the electron distribution analysis. I. Shell structure of atoms
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对电子分布分析的贡献。
DOI：
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
H. Preuss
中科院分区：
文献类型：
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作者：
M. Kohout;A. Savin;H. Preuss
计算了Be-Ba、B-Tl、C-Pb、Cu-Au和Zn-Hg原子的相对论球平均数值全电子密度ρ。在重原子的情况下，这些密度的拉普拉斯算子不能从第四行开始从内壳层解析价壳层。局部动能Ekin的分布甚至对于这些重原子也显示出价最大值，不幸的是，在负动能的区域中;即，非经典允许。此外，还研究了数量− <$$> ρ <$/ρ。对于所有计算的原子，− π π ρ π/ρ图都能够描述完整的壳层结构。− <$$> ρ <$/ρ对基组质量很敏感：较差的高斯基组会出现虚假振荡和过早的线性衰减。对于B-Tl、Ba、Au、Hg和Pb原子，进行了非相对论数值计算，以检查相对论对上述量的影响。用赝势密度进行的试验表明，赝势计算是可行的。
Relativistic spherically averaged numerical all‐electron densities ρ were computed for the atoms Be–Ba, B–Tl, C–Pb, Cu–Au, and Zn–Hg. The Laplacian of these densities is not able to resolve the valence shell from the inner shells in case of heavy atoms, starting with the fourth row. The distribution of the local kinetic energy Ekin shows a valence maximum even for these heavy atoms, unfortunately, in a region of negative kinetic energy; i.e., nonclassically allowed. The quantity −‖∇ρ‖/ρ was also investigated. For all computed atoms, the −‖∇ρ‖/ρ diagrams are capable of describing the complete shell structure. −‖∇ρ‖/ρ is sensitive to basis set quality: poor Gaussian basis sets exhibit spurious oscillations and a premature onset of the linear decay. For the atoms B–Tl, Ba, Au, Hg, and Pb, nonrelativistic numerical calculations were performed to examine the effect of the relativity on the aforementioned quantities. Tests with pseudopotential densities reveal that for pseudopotential calculations, it is advisa...