Mixed 5f configuration in americium trichloride: Dynamical mean-field theory combined with density functional theory study

The electronic properties in particular the occupation number of 5f electrons and the valence state of Am ions in americium trichloride (AmCl3) are studied by using density functional theory (DFT) merged with dynamical mean-field theory (DMFT). We find that j = 5/2, j = 7/2 manifolds both are in the insulating regimes, resulting in the semiconducting band gap of about 0.837 eV, together with the weak Am 5f-conduction electrons hybridization and the localized 5f-derived spectra feature in the vicinity of the Fermi level. The weighted summation for the occupation probabilities of 5f(n) (n = 3-7) atomic configurations suggests that 5f electrons have the interconfiguration fluctuation with an average occupation number of 5f electrons n(5f) similar to 5.182, corresponding to the valence state of Am3.818+ in AmCl3. The 5fn-mixing-driven inter-configuration fluctuation might originate from the complicated quantum mechanics processes such as the dual nature of 5f electrons and the flexible electronic configuration of Am ions. Finally, the so-called quasiparticle band structure is also predicted.

Automated summary

In this study, the electronic properties, specifically the occupation number of 5f electrons and the valence state of Am ions in Americium trichloride (AmCl3), were investigated using density functional theory (DFT) combined with dynamical mean-field theory (DMFT). The results showed that both j = 5/2 and j = 7/2 manifolds were in the insulating regime, resulting in a semiconductor band gap of approximately 0.837 eV. Additionally, weak hybridization between Am 5f-conduction electrons and the localized 5f-derived spectra near the Fermi level was observed. The occupation probabilities of 5f(n) (n = 3-7) atomic configurations suggested that the 5f electrons exhibited interconfiguration fluctuation with an average occupation number of 5f electrons (n(5f)) of around 5.182, corresponding to the valence state of Am3.818+ in AmCl3. The interplay between 5fn mixing and electronic configuration flexibility of Am ions might be responsible for these fluctuations. The predicted quasiparticle band structure was also discussed.