Orbital mixing in CO chemisorption on transition metal surfaces

The chemisorption of CO on metal surfaces is widely accepted as a model for understanding chemical bonding between molecules and solid surfaces, but is nevertheless still a controversial subject. Ab initio total energy calculations using density functional theory with gradient corrections for CO chemisorption on an extended Pd{110} slab yield good agreement with experimental adsorption energies. Examination of the spatial distribution of individual Bloch states demonstrates that the conventional model for CO chemisorption involving charge donation from CO 5σ states to metal states and back-donation from metal states into CO 2π states is too simplistic, but the computational results provide direct insight into the chemical bonding within the framework of orbital mixing (or hybridisation). The results provide a sound basis for understanding the bonding between molecules and metal surfaces.