Armbruster Markus K, Weigend Florian, van Wüllen Christoph, Klopper Wim
Forschungszentrum Karlsruhe GmbH, Institut für Nanotechnologie, P. O. Box 3640, D-76021, Karlsruhe, Germany.
Phys Chem Chem Phys. 2008 Apr 7;10(13):1748-56. doi: 10.1039/b717719d. Epub 2008 Feb 14.
Efficient self-consistent field (SCF) schemes including both scalar relativistic effects and spin-orbit (SO) interactions at Hartree-Fock (HF) and density functional (DFT) levels are presented. SO interactions require the extension of standard procedures to two-component formalisms. Efficiency is achieved by using effective core potentials (ECPs) and by employing the resolution-of-the-identity approximation for the Coulomb part (RI-J) in pure DFT calculations as well as also for the HF-exchange part (RI-JK) in the case of HF or hybrid-DFT treatments. The procedures were implemented in the program system TURBOMOLE; efficiency is demonstrated for comparably large systems, such as Pb54. Relevance of SO effects for electronic structure and stability is illustrated by treatments of small Pb and Po clusters with and without accounting for SO effects.
本文提出了在Hartree-Fock（HF）和密度泛函（DFT）水平上包含标量相对论效应和自旋轨道（SO）相互作用的高效自洽场（SCF）方案。SO相互作用需要将标准程序扩展到双组分形式体系。通过使用有效核势（ECP）以及在纯DFT计算中对库仑部分采用单位分解近似（RI-J），在HF或杂化DFT处理中对HF交换部分也采用单位分解近似（RI-JK）来实现效率提升。这些程序已在程序系统TURBOMOLE中实现；对于相当大的体系，如Pb54，展示了其效率。通过对有无考虑SO效应的小Pb和Po团簇的处理，说明了SO效应与电子结构和稳定性的相关性。
