Turbomole GmbH, Litzenhardtstraße 19, 76135 Karlsruhe, Germany.
J Chem Phys. 2017 Aug 7;147(5):054101. doi: 10.1063/1.4995614.
The quaternionic formulation of the time-reversal invariant quasirelativistic Kohn-Sham equations with exact Hartree-Fock exchange leads to hypercomplex one-component equations with half of the dimension compared to the original two-component problem. The combination of the quaternionic equations with point group symmetry exploitation for D and its subgroups by construction of corepresentations leads to quaternionic, complex, or real algorithms depending on the structure of the point group. In this work, the quaternionic approach with point group symmetry exploitation of the relativistic four-component Dirac-Hartree-Fock theory by Saue and Jensen [J. Chem. Phys. 111, 6211 (1999)] will be adopted to the quasirelativistic two-component Kohn-Sham scheme for closed-shell systems. The implementation in the program system TURBOMOLE is applied to the large lead cluster Pb as a test case.
四元数形式的时间反演不变拟相对论 Kohn-Sham 方程与精确 Hartree-Fock 交换导致了超复数单分量方程，与原始的双分量问题相比，其维数减少了一半。通过构造核心表示，将四元数方程与点群对称性相结合，用于 D 及其子群，这导致了四元数、复数或实数算法，具体取决于点群的结构。在这项工作中，Saue 和 Jensen [J. Chem. Phys. 111, 6211 (1999)] 将相对论四分量 Dirac-Hartree-Fock 理论的点群对称性利用的四元数方法应用于封闭壳层系统的拟相对论双分量 Kohn-Sham 方案。该程序系统 TURBOMOLE 中的实现应用于大型铅团 Pb 作为测试案例。
