Variational Relativistic Two-Component Complete-Active-Space Self-Consistent Field Method

The accurate description of the electronic structure of transition metals and their compounds can be complicated by both the large number of close-lying states that often have multiconfigurational nature and significant relativistic effects. In order to address these challenges we present a two-comp...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2019-05, Vol.15 (5), p.2974-2982
Main Authors: Jenkins, Andrew J, Liu, Hongbin, Kasper, Joseph M, Frisch, Michael J, Li, Xiaosong
Format: Article
Language:English
Subjects:
Chemistry
Completeness
Dirac equation
Electron spin
Electronic structure
Optimization
Physics
Relativism
Relativistic effects
Self consistent fields
Spin-orbit interactions
Transition metals
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Summary:The accurate description of the electronic structure of transition metals and their compounds can be complicated by both the large number of close-lying states that often have multiconfigurational nature and significant relativistic effects. In order to address these challenges we present a two-component complete-active-space self-consistent field method that includes scalar relativistic effects and one-electron spin–orbit coupling during the self-consistent wave function optimization procedure. These relativistic effects are included via an “exact two-component” transformation of the solution of the one-electron modified Dirac equation. The method is applied to the study of spin–orbit splitting of ground and low-lying excited states of main group elements and selected transition metals.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.9b00011