| Autor: |
Thyssen, Jørn, Fleig, Timo, Jensen, Hans Jørgen Aa. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 7/21/2008, Vol. 129 Issue 3, p034109, 14p, 5 Charts, 1 Graph |
| Abstrakt: |
A new direct relativistic four-component Kramers-restricted multiconfiguration self-consistent-field (KR-MCSCF) code for molecules has been implemented. The program is based upon Kramers-paired spinors and a full implementation of the binary double groups (D2h* and subgroups). The underlying quaternion algebra for one-electron operators was extended to treat two-electron integrals and density matrices in an efficient and nonredundant way. The iterative procedure is direct with respect to both configurational and spinor variational parameters; this permits the use of large configuration expansions and many basis functions. The relativistic minimum-maximum principle is implemented in a second-order restricted-step optimization algorithm, which provides sharp and well-controlled convergence. This paper focuses on the necessary modifications of nonrelativistic MCSCF methodology to obtain a fully variational KR-MCSCF implementation. The general implementation also allows for the use of molecular integrals from a two-component relativistic Hamiltonian as, for example, the Douglas–Kroll–Hess variants. Several sample applications concern the determination of spectroscopic properties of heavy-element atoms and molecules, demonstrating the influence of spin-orbit coupling in MCSCF approaches to such systems and showing the potential of the new method. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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