Atomic oxygen adsorption on 3.125 at.% Ga stabilized δ-Pu (111) surface

All-electron density functional theory was used to investigate atomic oxygen adsorption on a gallium stabilized delta-plutonium (111) surface. High symmetry on-surface and interstitial adsorption sites, along with local environment (as determined by the absence or presence of gallium) were explored. The calculations comprised full structural relaxations. Spin-orbit-coupling was also taken into account to assess the complexity of absorbate-substrate interactions. We observed that O adsorbate prefers to bind strongly to a gallium deficient environment, with the most stable site being the threefold hollow fcc site and associated chemisorption energy of -5.06 eV. The binding energies were least favored when gallium is a nearest neighbor to the O adsorbate, suggesting that the presence of gallium in a plutonium matrix tends to slow down the oxide layer growth. Although the oxygen coordination is the highest in the interstitial sites, the adsorption energy is less favored compared to on-surface adsorption, implying that the diffusion of oxygen from the surface layer into the subsurface layers is an activated process. The adsorption process induced non-trivial deformations of the surface. Additionally, some delocalization of the plutonium 5f and 6d partial electron density of states (PDOS) at the Fermi energy was observed. Further analysis in the PDOS indicated that gallium tends to suppress hybridization between the plutonium 5f and oxygen 2p orbitals, while the 6d orbitals hybridized with oxygen 2p orbitals. Published by Elsevier B.V.