This Is AuburnAUrora

Delocalized water and fluoride contributions to Dyson orbitals for electron detachment from the hydrated fluoride anion


Canuto, Sylvio
Coutinho, Kaline
Cabral, Benedito J. C.
Zakrzewski, V. G.
Ortiz, J.V.


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 H2O 1b1 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 .