Extended Douglas-Kroll transformations applied to the relativistic many-electron Hamiltonian

被引：80

作者：

Nakajima, T ^{[1
]}

Hirao, K

机构：

[1] Univ Tokyo, Grad Sch Engn, Dept Appl Chem, Tokyo 1138656, Japan

[2] Japan Sci & Technol Corp, PRESTO, Tokyo 1138656, Japan

[3] Inst Mol Sci, Okazaki, Aichi 4448585, Japan

来源：

JOURNAL OF CHEMICAL PHYSICS | 2003年 / 119卷 / 08期

关键词：

D O I：

10.1063/1.1594173

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A new generalized Douglas-Kroll (DK) approach is proposed for the relativistic many-electron Hamiltonian including the electron-electron interaction. In order to consider the higher-order DK transformation to the two-electron interaction, the present approach adopts the effective one-electron potential in the Dirac-Hartree-Fock/Dirac-Kohn-Sham operator as an expansion parameter in the DK transformation. Its numerical performance is tested for the atomic Hg and molecular HAt and At-2 systems. The third-order DK transformation to both one-electron and two-electron Hamiltonians, which is the highest level of theory treated in this study, gives excellent agreement with the four-component relativistic approach. The first-order DK correction to the two-electron interaction is shown to be satisfactory for both atomic and molecular systems. (C) 2003 American Institute of Physics.

引用

页码：4105 / 4111

页数：7

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