An ab initio method for high accuracy calculations for atoms with more than one valence electron is described. The effective Hamiltonian for the valence electrons is formed using many-body perturbation theory for the interaction of the valence electrons with the core. The configuration-interaction method is then used to find the energy levels of the atom. An application of this to thallium shows that the method gives an accuracy of about 0.5% for the ionization potential and a few tenths of a percent for the first few energy intervals. © 1996 The American Physical Society.

• Received 6 March 1996

DOI:https://doi.org/10.1103/PhysRevA.54.3948