Crystal field surface orbital-bond energy bond order (CFSO-BEBO) calculations of adsorption: II. Carbon monoxide,oxygen and carbon dioxide on platinum (111) and oxygen on nickel (111)

The Crystal Field Surface Orbital-Bond Energy Bond Order (CFSO-BEBO) model of chemisorption is applied to the interaction of carbon monoxide, oxygen and carbon dioxide with a (111) platinum surface; and the interaction of oxygen with a (111) nickel surface. No activation energy for molecular adsorption of carbon monoxide on platinum is predicted; however a large activation energy for dissociative chemisorption is calculated. The molecular state has a binding energy of approximately 28 kcal/mole, and vibrational stretching frequencies of 1935 and 1975 cm^?1 are calculated by combining the CFSO-BEBO model with Badger's Rule. The adsorption of oxygen on (111) platinum and (111) nickel are predicted to be different in the following respects: (1) There is an activation energy of 2.1–4.5 kcal/mole on platinum, whereas adsorption on nickel is unactivated; and (2) The dissociative heat of chemisorption on platinum is 58–68 kcal/mole, whereas on nickel it is substantially larger, 112–116 kcal/mole. The adsorption of carbon dioxide on (111) platinum is predicted to be not only highly activated but also endothermic. All of the calculated results are essentially in quantitative agreement with available experimental data.