Article ID Journal Published Year Pages File Type
221517 Journal of Electroanalytical Chemistry 2006 11 Pages PDF
Abstract

Quantum effects in the kinetics of the reaction O2+e→O2- have been evaluated theoretically. The spectral properties and the potential energy curves of the oxygen molecule and the superoxide ion were obtained from quantum DFT calculations at the G96PW91/6-311+G* level. From these curves, the vibrational eigenfunctions and eigenvalues of the reactant and the product were calculated. The corresponding non-adiabatic reduction rate was obtained from first-order perturbation theory. The partial contributions coming from the ground and excited states of both species are analyzed in detail. It is shown that the contribution of the O2- excited states to the rate is negligibly small for low overpotentials. Their participation rises when higher overpotentials are applied.

Related Topics
Physical Sciences and Engineering Chemical Engineering Chemical Engineering (General)
Authors
, , ,