Relativistic all-order and multiconfiguration Hartree-Fock calculations of the4d−4fenergy separation in Li I

Abstract

We present a calculation of the 4d-4f energy separation in Li I using two advanced techniques in atomic structure theory, namely, the relativistic all-order method and the multiconfiguration Hartree-Fock (MCHF) method. The accuracy of our calculations was investigated by conducting a third-order many-body perturbation theory calculation that allowed us to evaluate the importance of fourth- and higher-order corrections. A large-scale MCHF calculation was performed using the active space method and the core-polarization approximation. The obtained results provide an important test of these methods against each other and are shown to agree with the most accurate available experimental data.