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

共 24 条

[1] MATRIX REPRESENTATION OF THE RELATIVISTIC KINETIC-ENERGY OPERATOR - 2-COMPONENT VARIATIONAL PROCEDURE FOR THE TREATMENT OF MANY-ELECTRON ATOMS AND MOLECULES [J].

BUENKER, RJ ;

CHANDRA, P ;

HESS, BA .

CHEMICAL PHYSICS, 1984, 84 (01) :1-9

[2] QUANTUM ELECTRODYNAMICAL CORRECTIONS TO FINE-STRUCTURE OF HELIUM [J].

DOUGLAS, M ;

KROLL, NM .

ANNALS OF PHYSICS, 1974, 82 (01) :89-155

[3] THE ZORA FORMALISM APPLIED TO THE DIRAC-FOCK EQUATION [J].

FAAS, S ;

SNIJDERS, JG ;

VANLENTHE, JH ;

VANLENTHE, E ;

BAERENDS, EJ .

CHEMICAL PHYSICS LETTERS, 1995, 246 (06) :632-640

[4] ON THE DIRAC THEORY OF SPIN 1/2 PARTICLES AND ITS NON-RELATIVISTIC LIMIT [J].

FOLDY, LL ;

WOUTHUYSEN, SA .

PHYSICAL REVIEW, 1950, 78 (01) :29-36

[5]

Grant IP, 2000, INT J QUANTUM CHEM, V80, P283, DOI 10.1002/1097-461X(2000)80:3<283::AID-QUA2>3.0.CO

[6]

2-L

[7] RELATIVISTIC ELECTRONIC-STRUCTURE CALCULATIONS EMPLOYING A 2-COMPONENT NO-PAIR FORMALISM WITH EXTERNAL-FIELD PROJECTION OPERATORS [J].

HESS, BA .

PHYSICAL REVIEW A, 1986, 33 (06) :3742-3748

[8] An improved ab initio relativistic zeroth-order regular approximation correct to order 1/c2 [J].

Klopper, W ;

van Lenthe, JH ;

Hennum, AC .

JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (22) :9957-9965

[9] The electron-electron interaction in the Douglas-Kroll-Hess approach to the Dirac-Kohn-Sham problem [J].

Matveev, A ;

Rösch, N .

JOURNAL OF CHEMICAL PHYSICS, 2003, 118 (09) :3997-4012

[10] Numerical illustration of third-order Douglas-Kroll method: atomic and molecular properties of superheavy element 112 [J].

Nakajima, T ;

Hirao, K .

CHEMICAL PHYSICS LETTERS, 2000, 329 (5-6) :511-516

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