Nonadiabatic Pathways in the Dissociative Adsorption of Simple Molecules.
Mol. beams and laser spectrometry were used to study nonadiabatic processes in the interaction of mols. with well-characterized surfaces. The emission of exoelectrons and the formation of O⁻ ions in the interaction of O₂ mols. with a Cs(√3 * √3) structure on Ru(001) was studied as a function of translational energy, extending previously reported results. The interaction of O₂ with an Al(111) surface exhibits an abstraction channel, which is predominant at translational energies smaller than 0.5 eV. In the interaction of NO₂ with an Al(111) surface, the operation of an abstraction channel resulting in O(a) and NO(g) is obsd. All three examples are interpreted to indicate the significance of early charge transfer channels in mol. dissociative adsorption processes. Delayed charge transfer may lead to nonadiabatic reaction routes in this scenario.
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