Hartree–Foch wavefunctions (SCF) are calculated for neutral and ionic configurations of vanadium, and the 3d and 4s radial parts are compared in the various excited states. The 4s electrons show contraction effects, on ionization, stronger than those exhibited by ‘inner’ 3d orbitals.

Very little difference is found between the 3d radial parts of the wavefunctions corresponding to (3d^n–2) ionic and to (3d^n–24s²) neutral configurations, confirming the negligible effect of the ‘outer’s-orbitals on 3d.

The calculated transition-energies are compared with some available experimental data.