The electron attachment energy of the aqueous hydroxyl radical predicted from the detachment energy of the aqueous hydroxide anion.
Combining photoemission and electrochemical data from the literature we argue that the difference between the vertical and adiabatic ionization energy of the aqueous hydroxide anion is 2.9 eV. We then use density functional theory based molecular dynamics to show that the solvent response to ionization is nonlinear. Adding this to the experimental data we predict a 4.1 eV difference between the energy for vertical attachment of an electron to the aqueous hydroxyl radical and the corresponding adiabatic electron affinity. This places the state accepting the electron only 2.2 eV below vacuum or 7.7 eV above the edge of the valence band of water.
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Christopher
C
Adriaanse
Marialore
M
Sulpizi
Joost
J
VandeVondele
Michiel
M
Sprik