Electronic structure and properties of transition-metal–metalloid glasses: ${\mathrm{Ni}}_{1\mathrm{-}\mathrm{x}}$${\mathrm{P}}_{\mathrm{x}}$

The linear-muffin-tin-orbital method is used to study the electronic structure of ${\mathrm{Ni}}_{1\mathrm{-}\mathrm{x}}$ ${\mathrm{P}}_{\mathrm{x}}$, a prototype transition-metal–metalloid glass. Recent studies of c-${\mathrm{Ni}}_3$P and a-${\mathrm{Ni}}_3$P, based on the orthogonalized linear-combination-of-atomic-orbitals method, show that the densities of states of the two structures are quite similar. Because of this result and the complexity of the self-consistent spin-polarized calculations, the 16-atom cluster of c-${\mathrm{Ni}}_3$P is used to simulate the amorphous structure. The calculated results agree very well with the observed rapid decrease in the density of states at the Fermi level as x increases from 0.125 to 0.25. This rapid decrease in the density of states at the Fermi level with increasing x also explains the disappearance of a ferromagnetic phase transition in ${\mathrm{Ni}}_{1\mathrm{-}\mathrm{x}}$ ${\mathrm{P}}_{\mathrm{x}}$ glass for x greater than 0.18–0.19. The electronic structure responsible for the many interesting properties of a transition-metal–metalloid glass arises from a complex hybridization of transition-metal and metalloid orbitals.