Calculation of the coupling constants of many-electron atoms with external fields using expansions in a discrete basis of sturmian-type virtual orbitals

Abstract

Based on a generalization of the method of Sturmian expansions to the case of many-electron systems, a fundamentally new approach was developed for the construction of a complete set of intermediate states in many-body perturbation theory thereby avoiding integration over states of the continuous spectrum. A complete system of eigenfunctions of the generalized eigenvalue problem for the one-electron Hartree-Fock equation with a factor before the energy operator and fixed values of the Lagrange multipliers is used as a basis of single-particle virtual orbitals for an initial approximation to the eigenfunctions of the Hartree-Fock self-consistent field method. In the case of bound states, the spectrum of the effective operator is purely discrete, thus permitting one to completely eliminate integration over continuum virtual orbitals in applying methods of many-body perturbation theory to atomic and molecular calculations for a number of cases. As a consequence, one manages to avoid a number of the technical difficulties associated with inclusion of such states. The possibilities of the developed approach are illustrated in application to the investigation of the interaction of many-electron atoms with external fields.