Pressure-Driven 5f Localized-Itinerant Transition and Valence Fluctuation in Californium

Abstract

A combination of the density functional theory and the single-site dynamical mean-field theory is employed to study the pressure dependence of electronic structure for cubic phase californium. We predict that its 5f electrons could undergo an orbital-selective localized-itinerant transition under moderate pressure. The volume contraction causes remarkable charge redistribution and valence fluctuation behaviors, which are the driving forces of the divalent-trivalent transition. Additionally, we find that the angular momentum coupling mechanism is hardly affected by pressure. The 5f orbital occupancy is well described by the intermediate coupling scheme.

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