First-principles total-energy band calculations using the fixed-spin-moment procedure are used to study the volume dependence of the magnetic behavior for fcc Rh and Pd. We calculate the total energy, the magnetic moment, and the spin-polarized l-decomposed electron occupancy from below the equilibrium volume to the free-atom limit, and show the magnetic susceptibility in the nonmagnetic range. We find that both metals are nonmagnetic at zero pressure, but undergo first-order transitions from nonmagnetic to magnetic behavior at expanded volumes. In both cases, the onset of magnetic behavior is accompanied by magnetic moments that exceed the Hund’s-rule atomic limit. With increasing volume, we find a depletion of s and p states and a corresponding increase of d states with an approach to the 4$d^9$ and 4$d^{10}$ free-atom configurations for Rh and Pd, respectively.

• Received 14 September 1988

DOI:https://doi.org/10.1103/PhysRevB.39.471