Adsorption of CO on the rutile TiO2(110) surface: a dispersion-corrected density functional theory study

The geometry, energy and stretching frequency of carbon monoxide on the rutile TiO2(110) surface for coverages between 0.125 and 1.5 ML are investigated by means of density functional theory calculations. Four different approaches were considered, namely, the PBE exchange–correlation functional and the PBE-D2, vdW-DF and vdW-DF2 methods incorporating van der Waals dispersion interactions of different theoretical complexity and empiricism. It is found that upon the increase of the surface coverage, the adsorption becomes less favorable due to lateral destabilizing interactions between adsorbed molecules. The preferred geometry for CO changes from an upright configuration at 0.125 ML to tilted configurations at 1.5 ML and the tilting of the C–O axis from the surface normal increases with the increase of the surface coverage. At 1 ML, all computational approaches predict alternate tilted configurations which contradict the interpretation of recent experimental infrared reflection–absorption spectroscopic findings suggesting upright CO geometries. Encouragingly, a very good agreement between calculated and experimental shifts of the C–O stretching frequency of adsorbed CO at different coverages with respect to gaseous CO species was reached.