Generating optimal Sturmian basis functions for atomic problems

Abstract

In this paper we discuss the optimization of Sturmian basis functions by studying bound atomic systems within the configuration interaction method. Our investigation clearly shows how the fulfillment of correct physical boundary conditions at short and large distances from the nucleus improves the convergence rate of the method. This is illustrated first through a one-electron atom, and then with the two-electron systems. For the ground state of the helium atom, and with 35 Sturmian functions per electron and angular momenta, we obtain an energy of $\ensuremath{-}2.903 712 820$ a.u., outperforming previous similar calculations [Bromley and Mitroy, Int. J. Quantum Chem. 107, 1150 (2007)].