The experimental vertical electron detachment energy (VEDE) of aqueous fluoride, [F(H2O)], is approximately 9.8 eV, but spectral assignment is complicated by interference between F 2p and H2O1b1 orbitals. The electronic structure of [F(H2O)] 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(H2O)+] than as [F(H2O)].

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