Sturmian bases for two-electron systems in hyperspherical coordinates

TL;DR

This paper introduces new hyperangular sturmian functions for two-electron systems in hyperspherical coordinates, improving convergence and accuracy in calculating energy spectra and transition properties with fewer basis functions.

Contribution

The authors develop and analyze hyperangular sturmian functions that treat electron-electron correlation exactly, enhancing spectral calculations for two-electron atoms in hyperspherical coordinates.

Findings

Accurate energy levels for H$^-$ with smaller basis sets.

Precise electric-dipole oscillator strengths for helium transitions.

Comparable or better accuracy than state-of-the-art methods.

Abstract

We give a detailed account of an $\it{ab}$ $\it{initio}$ spectral approach for the calculation of energy spectra of two active electron atoms in a system of hyperspherical coordinates. In this system of coordinates, the Hamiltonian has the same structure as the one of atomic hydrogen with the Coulomb potential expressed in terms of a hyperradius and the nuclear charge replaced by an angle dependent effective charge. The simplest spectral approach consists in expanding the hyperangular wave function in a basis of hyperspherical harmonics. This expansion however, is known to be very slowly converging. Instead, we introduce new hyperangular sturmian functions. These functions do not have an analytical expression but they treat the first term of the multipole expansion of the electron-electron interaction potential, namely the radial electron correlation, exactly. The properties of these new functions are discussed in detail. For the basis functions of the hyperradius, several choices are possible. In the present case, we use Coulomb sturmian functions of half integer angular momentum. We show that, in the case of H$^-$, the accuracy of the energy and the width of the resonance states obtained through a single diagonalization of the Hamiltonian, is comparable to the values given by state-of-the-art methods while using a much smaller basis set. In addition, we show that precise values of the electric-dipole oscillator strengths for $S\rightarrow P$ transitions in helium are obtained thereby confirming the accuracy of the bound state wave functions generated with the present method.