Dynamical Valence Fluctuations and Magnetic Anisotropy in Sm(Co,Cu)$_5$

Abstract

The magnetic properties of Sm-based intermetallics are governed by a delicate interplay between localized $4f$ states, exchange interactions, and valence fluctuations, yet the role of dynamical $4f$ correlations remains poorly understood. Here we investigate the electronic structure and magnetic anisotropy of SmCo$_5$ and SmCu$_5$ using self-consistent DFT+$U$(ED), which explicitly treats dynamical fluctuations of the Sm $4f$ shell. We find that SmCo$_5$ exhibits pronounced Sm$^{2+}$--Sm$^{3+}$ valence fluctuations, with the $4f$ ground state dominated by $f^5$ and $f^6$ configurations. The resulting dynamical $4f$ correlations yield near compensation of the Sm spin and orbital moments and provide a quantitative description of the electronic structure, magnetic moments, and large uniaxial magnetic anisotropy of SmCo$_5$. Upon replacing Co with Cu, the balance shifts toward the $f^6$ configuration, with substantial changes in the Sm spin and orbital moments. In SmCu$_5$, this evolution of the $4f$ configuration is accompanied by a pronounced reduction of both the total magnetic moment and magnetic anisotropy. These results demonstrate that dynamical $4f$ valence fluctuations are essential for understanding the contrasting magnetic properties of SmCo$_5$ and SmCu$_5$ and provide a microscopic framework for describing magnetic anisotropy upon Co to Cu substitution in Sm(Co,Cu)$_5$.