CO adsorption energies on metals with correction for high coordination adsorption sites – A density functional study

We investigate the accuracy of carbon monoxide adsorption energies and site preferences for the metals Ag, Al, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Re, Rh, Ru, W, and Zn using the RPBE functional with a recently suggested empirical adsorption energy correction for carbon monoxide based on the internal CO stretch vibrational frequency. We find that when including the correction, the adsorption site preference for six of the metals changes, and all adsorption site predictions become accurate. We also collect a large number of experimental studies for comparison with our calculated adsorption energies. The mean absolute deviation including the correction is found to be less than 0.2 eV, showing that the RPBE functional gives a much better quantitative agreement between experiments and calculations than the PW91 functional.