Self-interaction Corrected Local Spin Density Theory of 5f Electron Localization in Actindes

TL;DR

This study applies a self-interaction corrected local spin density approach to investigate 5f electron behavior in actinides, revealing a transition from localized to delocalized states under compression, with implications for magnetic and structural properties.

Contribution

It introduces a method that captures dual 5f electron character and predicts localization-delocalization transitions in actinides, aligning with experimental volumes.

Findings

Predicts delocalization in early actinides and localization in later ones.

Shows a gradual localization-delocalization transition under compression.

Finds equilibrium volumes agree with experimental data.

Abstract

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 to describe a dual character of the 5f electrons, some of which occupy localized and core-like states, while the remaining 5f electrons hybridize and form bands. Based on energetics the calculations predict delocalization/paramagnetism in the early actinides, and localization/anti-ferromagnetism 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 desciption of cohesive properties. Under compression, in the later actinides, a localization-delocalization transition happens gradually as more and more f electrons become band-like with decreasing volume. Pu is already at this transition point at ambient conditions. Delocalization sets in for Am and Bk at a compression of $V\sim 0.75V_0$, for Cm at $V\sim 0.60 V_0$, where V_0 is the equilibrium volume, and the transition is complete for $V\sim 0.4-0.5 V_0$ in these three elements.