Self-interaction-corrected local spin density theory of 5f electron localization in actinides

The electronic structures of the actinide elements U, Np, Pu, Am, Cm, and Bk are investigated within the self-interaction-corrected local spin density approximation. This method allows us to describe a dual character of the 5f electrons, some of which occupy localized and corelike states, while the remaining 5f electrons hybridize and form bands. Based on energetics, the calculations predict delocalization and/or paramagnetism in the early actinides and localization and/or antiferromagnetism in the later actinides. The corresponding calculated equilibrium volumes are in agreement with the experimental values. For Pu and Am, the method wrongly predicts magnetic ordering, but we find that the paramagnetic state gives a better description of cohesive properties. Under compression, in the later actinides, a localization-delocalization transition happens gradually as more and more f electrons become bandlike with decreasing volume. Pu is already at this transition point at ambient conditions. Delocalization sets in for Am and Bk at a compression of V0.75V0, for Cm at V 0.60V0, where V0 is the equilibrium volume, and the transition is complete for V0.4‐0.5V0 in these three elements.