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Orthogonality-constrained SCF theory for singlet states with two open shells of equal symmetry

 

作者: Rolf Manne,   Knut Fægri,  

 

期刊: Molecular Physics  (Taylor Available online 1977)
卷期: Volume 33, issue 1  

页码: 53-61

 

ISSN:0026-8976

 

年代: 1977

 

DOI:10.1080/00268977700103041

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

The problem of calculating singlet states with two non-degenerate singly occupied orthogonality-constrained orbitals is investigated. The generalized Brillouin condition of Levy and Berthier leads to problems of accuracy and convergence and may even yield energies far below a variational upper bound. An alternative condition is formulated requiring the cancellation of energy contributions from the interaction with single excitations between the open shells. In calculations using this condition accuracy and convergence is considerably improved although strict upper bounds to the energy are not obtained. Test calculations for some simple molecules show the utility of the new method.

 

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