Armbruster Markus K, Klopper Wim, Weigend Florian
Center for Functional Nanostructures (CFN) and Lehrstuhl für Theoretische Chemie, Institut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany.
Phys Chem Chem Phys. 2006 Nov 14;8(42):4862-5. doi: 10.1039/b610211e. Epub 2006 Sep 22.
The accuracy of standard basis sets of quadruple-zeta and lower quality for the use in two-component self-consistent field procedures including spin-orbit coupling is investigated for the elements In-I and Au-At. Spin-orbit coupling leads to energetic and spatial splittings of inner shells, which are not described accurately with standard basis sets optimized for scalar relativistic calculations. This results in large errors in total atomic energies and significant errors in atomization energies of compounds containing these atoms. We show how these errors can be corrected by adding just a few steep sets of basis functions and demonstrate the quality of the resulting extended basis sets.
针对铟 - 碘（In - I）和金 - 砹（Au - At）元素，研究了用于包含自旋 - 轨道耦合的二分量自洽场程序的四重ζ及更低质量标准基组的准确性。自旋 - 轨道耦合导致内壳层的能量和空间分裂，而针对标量相对论计算优化的标准基组无法准确描述这些分裂。这导致总原子能量出现大的误差，以及含有这些原子的化合物的原子化能量出现显著误差。我们展示了如何通过仅添加几组陡峭的基函数来校正这些误差，并证明了所得扩展基组的质量。
