Abstract
The chemisorption of a hydrogen atom on a transition-metal surface is treated theoretically on the basis of the Anderson Hamiltonian in Hartree-Fock approximation, which includes the interelectronic interaction within the orbital. One-electron theory is shown to be inadequate for this problem. The localized states which may occur are discussed. A simple expression for the chemisorption energy is obtained, and a variational method is given for obtaining its self-consistent value. The metal eigenfunctions enter only through a function , and the foregoing results are exemplified and applied when this function is semielliptical. When the band is half-filled, a single analytic formula for the one-electron part of is obtained, in accord with the Kohn-Majumdar theorem. With some further assumptions, and the charge on the atom are calculated for adsorption on Ti, Cr, Ni, and Cu. The values of the hopping integral between the orbital and a neighboring metal orbital required to fit the experimental are found to be similar and are reasonable. The correct prediction that is believed to be significant. A suggestive correlation is found between observations of catalytic ortho-para hydrogen interconversion on Pd-Au alloys and a rigidband calculation of .
- Received 15 July 1968
DOI:https://doi.org/10.1103/PhysRev.178.1123
©1969 American Physical Society