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Correlated one‐electron wave functions
Author(s) -
Weiner B.,
Ortiz J. V.
Publication year - 2005
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.20607
Subject(s) - geminal , wave function , atomic orbital , electron , chemistry , density matrix , quantum mechanics , atomic physics , density functional theory , ionization energy , spin (aerodynamics) , basis set , operator (biology) , electronic correlation , slater determinant , physics , ionization , quantum , ion , thermodynamics , stereochemistry , biochemistry , repressor , gene , transcription factor
A one‐electron theory of many‐electron systems that explicitly describes electron–electron correlation may be based on the observation that antisymmetrized geminal power (AGP) states are completely characterized by the occupation numbers of their first‐order reduced density operators (FORDO) and a set of canonical general spin–orbitals (CGSOs), which are in general distinct from the natural general spin–orbitals. Because the FORDO alone does not determine an AGP state, a density matrix functional may be defined. A generalization of the independent‐particle Fock operator serves to express the total state energy in terms of ionization energies, kinetic energies, and potential energies of the CGSOs. A one‐electron picture of chemical bonding emerges from this theory. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005