Roles of 6d states on the atmospheric corrosion mechanisms of uranium

摘要

Surface hydrogenation, oxidation, and other corrosion -related reactions of uranium have attracted continuous concern for many years, because these processes are not only of great scientific interest, but also of significant practical importance for nuclear industries. Through several theoretical studies, we reveal that the 6d electronic states play important roles on the chemical properties of uraniu m. Our research progress can be summarized as follows: i) On γ -U surface, H 2 molecules dissociate barrierlessly due to s-d electronic hybridizations; ii) On α-U surface, there are also “s-d interaction” adsorption channels along which H 2 molecules dissociate barrierlessly; iii) Interactions between the three frontier molecular orbitals with surface d states lead to that H 2O dissociate spontaneously on the γ -U surface; iv) U -6d state is the only evolving state in different UnOm clusters, which hybridizes wit h U-5f states in U -rich clusters, and hybridizes with O-2p states in O-rich clusters.