MODEL STUDIES OF THE CHEMISORPTION OF HYDROGEN AND OXYGEN ON CU(100)

Journal article, 1987

Atomic chemisorption of hydrogen and oxygen on Cu(100) has been studied using up to 25 copper atoms as a model of the surface. The computational procedure used involves a reduction of the metal atoms to one-electron systems and extensive configuration-interaction calculations of the adsorbate and the cluster-adsorbate bonds. The calculations support the fourfold hollow site as the preferred chemisorption site for oxygen, with a barrier-to-surface migration of 25 kcal/mol. The calculated chemisorption energies for both hydrogen and oxygen, 51 and 90 kcal/mol, respectively, are in good agreement with experimental estimates (56 kcal/mol for hydrogen and 97 kcal/mol for oxygen). The effects of reducing the metal atoms to one-electron systems have been investigated through comparisons with all-electron calculations for Cu5H and Cu5O at the self-consistent-field level and by comparisons to previous calculations on Cu5Cl and Cu9Cl in which the 3d electrons were treated explicitly.