Local-density approximation: Cohesion in the transition metals ands→dpromotion in the transition-metal atoms

Systematics in cohesive energies (${\mathit{H}}_{\mathrm{coh}}$) and d–non-d atomic promotion energies have been examined for the transition elements treated within the local-density approximation (LDA). Cohesive energies involve the energy of the solid as compared with that of a reference state in the free atom; going from one atomic configuration to another (e.g., ${\mathit{d}}^{\mathit{n}\mathrm{-}2}$ ${\mathit{s}}^2$→${\mathit{d}}^{\mathit{n}\mathrm{-}1}$s) for that reference state involves a promotion energy. Errors in the LDA’s ability to calculate promotion energies are then translated into changes in calculated ${\mathit{H}}_{\mathrm{coh}}$. Employing the local-spin-density approximation (LSDA), scalar-relativistic values of the promotion energies have been obtained for atomic states of maximum spin multiplicity of the neutral atoms in the 3d, 4d, and 5d rows for those configurations for which experimental spectral data are available for comparison. The intent is that by scanning all three rows and those cases for which there are experimental data that those factors contributing to the LDA’s shortcomings in describing electron-electron interactions in the transition elements may become better defined.