d Orbitals in excited configurations of chlorine

Abstract

The energies and radial forms of 3d orbitals in the chlorine atom are calculated (i) in the ‘state’ of average energy for configurations s²p⁴d, sp⁵d, s²p³d², sp⁴d², and sp³d³, (ii) in selected multiplet terms of the d¹ and d² configurations, (iii) in the multiconfigurational valence state in ClF₃, and (iv) in the valence state of the atom in the electrostatic field of the fluorine atoms. Results are given for double-zeta radial wave-functions and compared with those for Slater (single-zeta) functions.

Features found earlier in d¹ and d² configurations of phosphorus and sulphur are confirmed. In d¹ the orbitals are diffuse, and approximately of Slater form. The term energies are confined to a narrow energy range. In d² the orbitals are contracted and more complex in radial form. The terms are also much more widely spread in energy. The ligand field strongly contracts the d-electrons of the valence state.