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Density matrix methods in orbital optimization for MCSCF calculations
Author(s) -
Garrod Claude
Publication year - 1978
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560130608
Subject(s) - basis (linear algebra) , eigenfunction , convergence (economics) , operator (biology) , mathematics , matrix (chemical analysis) , density matrix , consistency (knowledge bases) , physics , mathematical analysis , computational chemistry , quantum mechanics , eigenvalues and eigenvectors , chemistry , geometry , quantum , biochemistry , repressor , chromatography , transcription factor , economics , gene , economic growth
The problem considered is that of selecting the finite orbital basis which will minimize the energy in a given size CI calculation. (1) A one‐body operator is defined which has as eigenfunctions the desired optimal basis. The operator is defined in terms of the basis which leads to a self‐consistency problem of Hartree‐Fock type. (2) A method of successive orbital rotations is defined which is shown to have desirable convergence properties.