An improved ab initio relativistic zeroth-order regular approximation correct to order 1/c2
| Autor: | Joop H. van Lenthe, Alf C. Hennum, Wim Klopper |
|---|---|
| Rok vydání: | 2000 |
| Předmět: |
Physics
biology Ab initio General Physics and Astronomy biology.organism_classification Quantum chemistry Zeroth order Dipole symbols.namesake Zeroth law of thermodynamics Ab initio quantum chemistry methods Quantum electrodynamics Quantum mechanics symbols Physics::Atomic Physics Physical and Theoretical Chemistry Hamiltonian (quantum mechanics) Iora |
| Zdroj: | The Journal of Chemical Physics. 113:9957-9965 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.1323266 |
| Popis: | The equations of the original ab initio scalar-relativistic zeroth-order regular approximation (ZORA) and the infinite-order regular approximation (IORA) are expanded in orders of 1/c2. It is shown that previous ZORA/IORA implementations in ab initio quantum chemistry programs were not correct to order 1/c2, but contained imperfections leading to fictitious self-interactions. These errors can be avoided by adding exchange-type terms (coupling the large and small components) to the relativistic ZORA correction to the Hamiltonian, yielding improved ab initio relativistic zeroth- and infinite-order regular approximations that are correct to order 1/c2. The new methods have been tested numerically by computing the total energies, orbital energies, and static electric dipole polarizabilities of the rare gas atoms He through Xe. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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