title: Connection of DFT molecular orbital eigenvalues with the observable oxidation potentials/oxidation energies.
abstract: It is demonstrated that the negative highest occupied molecular orbital eigenvalues of a molecule S in the gas phase, -HOMO(S,g), and in solution, -HOMO(S,s), and the negative lowest unoccupied molecular orbital eigenvalue of its cation S(+) in solution, -LUMO(S(+),s), are good approximations to the oxidation energy, the energy for removing an electron out of a molecule in solution. This observation is based on the DFT calculations using the B3LYP exchange-correlation functional with a basis set of 6-311+G(d,p) and the polarizable continuum model (PCM) for computing solvation energies for a set of 22 middle-size molecules/radicals.
authors.affiliation: Department of Physics, East China University of Science and Technology , Shanghai, China 200237.
authors.forename: Jiang-Hua
authors.initials: JH
authors.lastname: Chen
authors.forename: Li-Ming
authors.initials: LM
authors.lastname: He
authors.forename: Richard L
authors.initials: RL
authors.lastname: Wang