  The segregation behavior of Cr in dilute Fe-Cr alloys is known to be
anomalous since the main barrier for surface segregation of Cr in these alloys
arises not from the topmost surface layer but from the subsurface layer where
the solution energy of Cr is much more endothermic as compared to the topmost
surface layer. The Fe-Cr alloys are candidate structural materials for the new
generation of nuclear reactors. The surfaces of these alloys will be exposed to
hydrogen or its isotopes in these reactors, and although hydrogen is soluble
neither in Fe nor in Fe-Cr alloys, it is known that the adsorption energy of
hydrogen on the surface of iron is not only exothermic but relatively large.
This clearly raises the question of the effect of the hydrogen adsorbed on the
surface of iron on the segregation behavior of chromium towards the surface of
iron. In this paper we show, on the basis of our ab initio density functional
theory calculations, that the presence of hydrogen on the surface of iron leads
to a considerably reduced barrier for Cr segregation to both the topmost
surface layer and the subsurface layer, but the subsurface layer still controls
the barrier for surface segregation. This reduction in the barrier for surface
segregation is due to the nature of the Cr-H couple that acts in a complex and
synergistic manner. The presence of Cr enhances the exothermic nature of
hydrogen adsorption that in turn leads to a reduced barrier for surface
segregation. These results should be included in the multiscale modeling of
Fe-Cr alloys.
