Accurate Scaling Functions of the Scaled Schrödinger Equation. II. Variational Examination of the Correct Scaling Functions with the Free Complement Theory Applied to the Helium Atom.

Abstract

In a previous paper [Phys. Rev. Lett. 2004, 93, 030403.], one of the authors introduced the scaled Schrödinger equation (SSE), g(H - E)ψ = 0 for atoms and molecules, where the scaling function g is the positive function of the electron-nuclear (e-n) and electron-electron (e-e) distances. The SSE is equivalent to the Schrödinger equation (SE), (H - E)ψ = 0, that governs the chemical world but does not have the divergence difficulty that occurs when we try to solve the SE to obtain the exact solution. The g function is essential not only to prevent this divergence difficulty but also to obtain the exact wave function of the SE or SSE. In paper I of this series [J. Chem. Phys. 2022, 156, 014113.], we introduced five analytical g functions that behave correctly at both the coalescence and asymptotic regions, but we examined them only for the e-e part. In this paper, we examine these correct g functions for both e-n and e-e parts by applying the free complement (complete-element) (FC) theory variationally to the He atom. However, even for the two-electron He atom, the analytical integral formulas were not obtained when we use the correct g functions for both e-n and e-e parts, except for g = 1 - exp(-γr), but we were able to perform variational FC calculations by employing numerical integration schemes. We examined not only the energy and wave function but also the H-square error (defined by eq 14 of the text), energy lower bound, and e-n and e-e cusp properties. For the energy lower bound, we applied our FC wave functions to the method proposed recently by Pollak, Martinazzo, and others and could obtain good results. With the use of the correct-group g functions, the convergence of the FC theory to the exact analytical solution of the SE or SSE became efficient, and the performance was particularly good with the g functions, r/(r + 1/γ), Ei, and 1 - exp(-γr) in this order. These results were always superior to those obtained with g = r.