Delocalized water and fluoride contributions to Dyson orbitals for electron detachment from the hydrated fluoride anion.
The experimental vertical electron detachment energy (VEDE) of aqueous fluoride, [F(-)(H(2)O)], is approximately 9.8 eV, but spectral assignment is complicated by interference between F(-) 2p and H(2)O 1b(1) orbitals. The electronic structure of [F(-)(H(2)O)] is analyzed with Monte Carlo and ab initio quantum-mechanical calculations. Electron-propagator calculations in the partial third-order approximation yield a VEDE of 9.4 eV. None of the Dyson orbitals corresponding to valence VEDEs consists primarily of F 2p functions. These results and ground-state atomic charges indicate that the final, neutral state is more appropriately described as [F(-)(H(2)O)(+)] than as [F(H(2)O)].
Canuto
Sylvio
S
Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970, São Paulo, SP, Brazil. canuto@if.usp.br
Coutinho
Kaline
K
Cabral
Benedito J C
BJ
Zakrzewski
V G
VG
Ortiz
J V
JV
D000838:Anions / Q000737:chemistry; D004583:Electrons; D005459:Fluorides / Q000737:chemistry*; D009010:Monte Carlo Method; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
D000838:Anions; D014867:Water; D005459:Fluorides