A singularity excluded approximate expansion scheme in relativistic density functional theory
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- 作者：Fan Wang and Le-min Li
- 关键词：Key words ; ; Quantum chemical calculations – ; Relativistic effects – ; Dirac operator – ; Approximate expansion – ; Density functional theory – ; Kohn ; Sham equation
- 刊名：Theoretical Chemistry Accounts ; Theory ; Computation ; and Modeling (Theoretica Chimica Acta)
- 出版时间：July 2002
- 出版年：2002
- 期刊代码：108_1432-881X
- 类别：ph
- 卷：108
- 期：1
- 页码：53-60
- 数据来源：sp
摘要
A singularity excluded approximate expansion (SEAX) scheme, which can be considered as one between Breit-Pauli expansion and RA expansion schemes, is proposed to expand the total energy of 4-component relativistic density functional theory. The one-electron equation can be derived variationally from the approximate total energy expression. The Hamiltonian of the one-electron equation is bounded from below and can be dealt with variationally, and the gauge dependency error in the ZORA method is essentially eliminated. It is easier to solve the SEAX equation than the IORA equation. The results related to the valence orbitals by solving the scalar SEAX equation agree very well with those by the scalar ZORA ESA method, and the results related to the inner-shell electrons of heavy elements by the two component SEAX calculations agree quite well with those by the 4-component relativistic density functional calculations.