The adsorption of methanol on aluminum (100) surface is modeled by quantum mechanical calculations on a small cluster, using hybrid Hartree-Fock / Density Functional Theory. The enthalpy of adsorption at low coverage is calculated for the high symmetry sites. The relevance of tipping of the prevalent methoxy species before C-O bond scission is examined. A new mechanism for dissociation is proposed, that is excellent agreement with experimental determinations of the energy of activation for dissociation. Principles of transition-state theory are correlated to theoretical calculation of vibrational frequencies. Current assumptions from molecular orbital theory, as applied to surface reaction energetics, are called into question.
© 2003-2012 by Lawrence T. Sein. All rights reserved.
Send questions to: lseinjr@hotmail.com