Abstract
The interaction of atomic and molecular hydrogen with the
actinide dioxide (AnO2, An = U, Np, Pu) (111) surfaces has been
investigated by DFT+U, where noncollinear 3k antiferromagnetic (AFM) behaviour
and spin-orbit interactions (SOI) are considered. The adsorption of atomic
hydrogen forms a hydroxide group, and is coupled to the reduction of an
actinide ion. The energy of atomic hydrogen
adsorption on the UO2 (0.82 eV), NpO2 (-0.10 eV), and PuO2
(-1.25 eV) surfaces has been calculated. The dissociation of molecular hydrogen
is not observed, and shown to be due to kinetic rather than thermodynamic
factors. As a barrier in the formation of a second hydroxyl group, an unusual charge
distribution has been shown. This is possibly a limitation of a (1·1) unit cell
method. The recombination of hydrogen ions on the AnO2 (111)
surfaces is favoured over hydroxide formation.