A Density Functional Study of Atomic Hydrogen Adsorption on Plutonium Layers

TL;DR

This study uses density functional theory to analyze hydrogen adsorption on delta-Pu (100) and (111) surfaces, revealing preferred adsorption sites, energies, and effects on magnetic moments and electronic structure.

Contribution

It provides detailed first-principles insights into hydrogen adsorption behavior on plutonium surfaces, including spin effects and electronic structure changes.

Findings

Center site is most favorable for adsorption.

Chemsorption energies are around 2.75-3.47 eV.

Hydrogen adsorption affects magnetic moments and work functions.

Abstract

Hydrogen adsorption on delta-Pu (100) and (111) surfaces using the generalized gradient approximation of the density functional theory with Perdew and Wang functionals have been studied at both the spin-polarized level and the non-spin-polarized level. For the (100) surface at the non-spin-polarized level, we find that the center position of the (100) surface is the most favorable site with a chemisorption energy of 2.762 eV and an optimum distance of the hydrogen adatom to the Pu surface of 1.07 A. For the spin-polarized (100) surface, the center site is again the preferred site with a chemisorption energy of 3.467 eV and an optimum hydrogen distance of 1.13 A. For the non-spin-polarized (111) surface, the center position is also the preferred site, but with slightly lower chemisorption energy, namely 2.756 eV and a higher hydrogen distance, 1.40 A, compared to the (100) center site. The center site is also the preferred site for the spin-polarized (111) surface, with a chemisorption energy of 3.450 eV and a hydrogen distance of 1.42 A. Also, for the spin-polarized calculations, the over all net magnetic moments of the (111) surface changed significantly due to the hydrogen adsorption. The 5f orbitals are delocalized, especially as one approaches the Fermi level. However, the degree of localization decreases for spin-polarized calculations. The coordination numbers have a significant role in the chemical bonding process. Mulliken charge distribution analysis indicates that the interaction of Pu with H mainly takes place in the first layer and that the other two layers are only slightly affected. Work functions, in general, tend to increase due to the presence of a hydrogen adatom.