Electronic Structures and Bonding of Oxygen on Plutonium Layers

TL;DR

This study uses density functional theory to analyze how oxygen atoms interact with delta-plutonium surfaces, revealing preferred adsorption sites, energies, and effects on electronic structure.

Contribution

It provides detailed computational insights into oxygen adsorption sites, energies, and electronic effects on plutonium surfaces using GGA-DFT methods.

Findings

Center site is most favorable for oxygen adsorption.

Chemisorption energies are around 7 eV for both surfaces.

Oxygen adsorption pushes plutonium 5f orbitals below the Fermi energy.

Abstract

Oxygen adsorption on delta-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 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 0.92A and 1.02A, 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 1.31A, 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.