  It is well known, both theoretically and experimentally, that alloying
MgH$_2$ with transition elements can significantly improve the thermodynamic
and kinetic properties for H$_2$ desorption, as well as the H$_2$ intake by Mg
bulk. Here we present a density functional theory investigation of hydrogen
dissociation and surface diffusion over Ni-doped surface, and compare the
findings to previously investigated Ti-doped Mg(0001) and pure Mg(0001)
surfaces. Our results show that the energy barrier for hydrogen dissociation on
the pure Mg(0001) surface is high, while it is small/null when Ni/Ti are added
to the surface as dopants. We find that the binding energy of the two H atoms
near the dissociation site is high on Ti, effectively impeding diffusion away
from the Ti site. By contrast, we find that on Ni the energy barrier for
diffusion is much reduced. Therefore, although both Ti and Ni promote H$_2$
dissociation, only Ni appears to be a good catalyst for Mg hydrogenation,
allowing diffusion away from the catalytic sites. Experimental results
corroborate these theoretical findings, i.e. faster hydrogenation of the Ni
doped Mg sample as opposed to the reference Mg or Ti doped Mg.
