Accurate calculation of spin-orbit coupling constants for 3d atoms and ions with effective core potentials and reduced basis sets.

Abstract

We present an approximate method for obtaining spin-orbit coupling constants of 3d atoms and ions from an effective one-body Hamiltonian. The method, suggested by numerical results of the analytical theory of Blume and Watson [Proc. R. Soc. London, Sect. A 270, 127 (1962); 271, 565 (1963)], incorporates the model potential approach of Bonifacic and Huzinaga [J. Chem. Phys. 60, 167 (1974)] for representing the core-valence interactions. In combination with reduced valence basis set, the new procedure gives accurate spin-orbit constants for the 3d atoms, and slightly less accurate values for di- and tripositive 3d ions. These results suggest that this method can be an accurate economic route to crystal calculations of the spin-orbit constants within any cluster-model approach involving the Hamiltonian of Misetich and Buch [J. Chem. Phys. 41, 2524 (1964)].