title: Methanol adsorption on the beta-Ga2O3 surface with oxygen vacancies: theoretical and experimental approach.
abstract: Methanol adsorption on beta-Ga2O3 surface has been studied by Fourier transform infrared spectroscopy (FTIR) and by means of density functional theory (DFT) cluster model calculations. Adsorption sites of tetrahedral and octahedral gallium ions with different numbers of oxygen vacancies have been compared. The electronic properties of the adsorbed molecules have been monitored by computing adsorption energies, optimized geometry parameters, overlap populations, atomic charges, and vibrational frequencies. The gallia-methanol interaction has different behaviors according to the local surface chemical composition. The calculations show that methanol can react in three different ways with the gallia surface giving rise to a nondissociative adsorption, a dissociative adsorption, and an oxidative decomposition. The surface without oxygen vacancies is very reactive and produces the methanol molecule decomposition. The molecule is nondissociatively adsorbed by means of a hydrogen bond between the alcoholic hydrogen atom and a surface oxygen atom and a bond between the alcoholic oxygen atom and a surface gallium atom. Two neighbor oxygen vacancies on tetrahedral gallium sites produce the dissociation of the methanol molecule and the formation of a bridge bond between two surface gallium atoms and the methoxy group.
authors.affiliation: Departamento de Física, Grupo de Materiales y Sistemas Catalíticos, Universidad Nacional del Sur, Av. Alem 1253, 8000, Bahía Blanca, Argentina. cabranda@criba.edu.ar
authors.forename: María M
authors.initials: MM
authors.lastname: Branda
authors.forename: Sebastian E
authors.initials: SE
authors.lastname: Collins
authors.forename: Norberto J
authors.initials: NJ
authors.lastname: Castellani
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Baltanas
authors.forename: Adrian L
authors.initials: AL
authors.lastname: Bonivardi