First-principles LDA+U and GGA+U study of neptunium dioxide

Abstract

We have performed a systematic first-principles investigation to calculate the electronic structures, mechanical properties, and phonon dispersion curves of NpO${}_2$. The local density approximation$+U$ and the generalized gradient approximation$+U$ formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Np $5f$ electrons. By choosing the Hubbard \emph{U} parameter around 4 eV, the orbital occupancy characters of Np 5\emph{f} and O 2\emph{p} are in good agreement with recent experiments [J. Nucl. Mater. \textbf{389}, 470 (2009)]. Comparing with our previous study of ThO${}_2$, we note that stronger covalency exists in NpO${}_2$ due to the more localization behavior of 5\emph{f} electrons of Np in line with the localization-delocalization trend exhibited by the actinides series.

7 pages, 6 figures