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Delocalization of Dyson orbitals in F − (H 2 O) and Cl − (H 2 O)
Author(s) -
Dolgounitcheva O.,
Zakrzewski V. G.,
Ortiz J. V.
Publication year - 2011
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.22705
Subject(s) - delocalized electron , atomic orbital , atomic physics , chemistry , linear combination of atomic orbitals , charge (physics) , spectral line , electron , molecular orbital , basis set , physics , character (mathematics) , computational chemistry , density functional theory , quantum mechanics , molecule , geometry , mathematics
Electron propagator calculations accurately predict the vertical electron detachment energies of the title complexes. Corresponding Dyson orbitals closely resemble canonical Hartree–Fock orbitals. Approximations that use diagonal self‐energies in the latter basis, therefore, show promise for applications on larger anionic clusters. Neutral final states correspond to Cl 3p or water 1b 1 holes, in accord with recent interpretations of Cl − (H 2 O) photoelectron spectra. However, for the F case, the Dyson orbitals are delocalized over the F and O centers and compromise interpretations that ascribe F(H 2 O) or F − (H 2 O + ) charge‐transfer character to the final states. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010