Experimental evidence on molecular interaction in desorption and adsorption of CO molecules on metal surfaces

Adsorption and desorption of CO on Ni(100) and Pt(111) surfaces are presented. At the thermodynamic equilibrium, the site occupation between the terminal and the bridged sites are described with the free energy of the system, including the vibrational entropy. Adsorption of CO onto a cold surface as 20 K has also been studied by infrared reflection absorption spectroscopy (IRAS). The occupation ratio of bridged CO to terminal CO species on Ni(100) at 20 K ranges from 2&middot8 to 0&middot7 at the total coverage from 0&middot003 to 0&middot15 ML. Such strong coverage dependence of the occupation ratio even at small coverages suggests that the interaction between CO molecules operates at relatively long range (> 10 A). The isotope experiments suggest that there is substantial interaction between preadsorbed (accommodated) CO species and incoming (mobile) CO species. Desorption process is also affected by the interaction between the adsorbed CO and the incoming species. The effect of temporal bimolecular CO interaction on the desorption kinetics is also discussed.