Artículos de revistas
Delocalized water and fluoride contributions to Dyson orbitals for electron detachment from the hydrated fluoride anion
Fecha
2010Registro en:
JOURNAL OF CHEMICAL PHYSICS, v.132, n.21, 2010
0021-9606
10.1063/1.3431081
Autor
Canuto, Sylvio Roberto Accioly
Coutinho, Kaline Rabelo
CABRAL, Benedito J. C.
ZAKRZEWSKI, V. G.
ORTIZ, J. V.
Institución
Resumen
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)]. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3431081]