  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.
