A singularity excluded approximate expansion scheme in relativistic density functional theory |
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| Authors: | Fan Wang Le-min Li |
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| Affiliation: | (1) State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China, CN |
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| Abstract: | 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. Received: 20 February 2002 / Accepted: 29 April 2002 / Published online: 8 July 2002 |
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| Keywords: | : Quantum chemical calculations – Relativistic effects – Dirac operator – Approximate expansion – Density functional theory – Kohn-Sham equation |
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