Lt. Sein et Sa. Jansen, ADSORPTION AND DISSOCIATION OF METHANOL ON ALUMINUM(100) - THEORETICAL-ANALYSIS OF REACTION-MECHANISM, JOURNAL OF PHYSICAL CHEMISTRY B, 102(13), 1998, pp. 2415-2418
The adsorption of methanol on aluminum (100) surface is modeled by qua
ntum mechanical calculations on a small cluster, using hybrid Hartree-
Fock/density functional theory. The enthalpy of adsorption at low cove
rage is calculated for the high-symmetry sites. The relevance of tippi
ng of the prevalent methoxy species before C-O bond scission is examin
ed. A new mechanism for dissociation is proposed, which is in excellen
t agreement with experimental determinations of the energy of activati
on for dissociation. Principles of transition-state theory are correla
ted to theoretical calculation of vibrational frequencies. Current ass
umptions from molecular orbital theory, as applied to surface reaction
energetics, are called into question.