Electronic structures and bonding of oxygen on plutonium layers

Oxygen adsorptions on -Pu (100) and (111) surfaces have been studied at both non-spin-polarized and spin-polarized levels using the generalized gradient approximation of density functional theory (GGA-DFT) with Perdew and Wang (PW) functionals. The center position of the (100) surface is found to be the most favorable site with chemisorption energies of 7.386 eV and 7.080 eV at the two levels of theory. The distances of the oxygen adatom from the Pu surface are found to be 0.92 Å and 1.02 Å, respectively. For the (111) surface non-spin-polarized calculations, the center position is also the preferred site with a chemisorption energy of 7.070 eV and the distance of the adatom being 1.31 Å, but for spin-polarized calculations the bridge and the center sites are found to be basically degenerate, the difference in chemisorption energies being only 0.021 eV. In general, due to the adsorption of oxygen, plutonium 5f orbitals are pushed further below the Fermi energy, compared to the bare plutonium layers. The work function, in general, increases due to oxygen adsorption on plutonium surfaces.Received: 20 July 2004, Published online: 9 September 2004PACS: 71.15.-m Methods of electronic structure calculations - 71.15.Mb Density functional theory, local density approximation, gradient and other corrections - 71.15.Nc Total energy and cohesive energy calculations 71.27. + a Strongly correlated electron systems; heavy fermions