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Delocalization of Dyson orbitals in F(H2O) and Cl(H2O)



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 1b1 holes, in accord with recent interpretations of Cl(H2O) photoelectron spectra. However, for the F case, the Dyson orbitals are delocalized over the F and O centers and compromise interpretations that ascribe F(H2O) or F(H2O+) charge-transfer character to the final states. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010