Ultra-Compact accurate wave functions for He-like and Li-like iso-electronic sequences and variational calculus. II. Spin-singlet (excited) and spin-triplet (lowest) states of the Helium sequence

TL;DR

This paper develops ultra-compact wave functions for excited states of He-like ions, achieving high accuracy in energy calculations and confirming nodal surface properties, extending previous ground state work to excited states with Z up to 20.

Contribution

It introduces new generalized Hylleraas-Kinoshita wave functions for excited states of He-like ions, providing high-precision energies and extending nodal surface analysis.

Findings

Accurate energy calculations for excited states with 4-5 significant digits.

Confirmation and extension of nodal surface properties for He-like ions.

Estimation of critical charges where wave functions lose square-integrability.

Abstract

As a continuation of Part I \cite{Part-1:2020} (Int. Journal of Quantum Chem. 2021; 121: qua.26586), dedicated to the ground state of He-like and Li-like isoelectronic sequences for nuclear charges $Z \leq 20$, a few ultra-compact wave functions in the form of generalized Hylleraas-Kinoshita functions are constructed, which describe the domain of applicability of the Quantum Mechanics of Coulomb Charges (QMCC) for the energies (4-5 significant digits (s.d.)) of two excited states of He-like ions: the spin-singlet (first) excited state $2^1 S$ and the lowest spin-triplet $1^3 S$ state. For both states it provides absolute accuracy for energy $\sim 10^{-3}$\,a.u., exact values for cusp parameters and also for 6 expectation values the relative accuracy $\sim 10^{-2}$. The Bressanini-Reynolds observation about the special form of the nodal surface of the $2^1 S$ state of Helium is confirmed and extended to He-like ions with $Z > 2$. Critical charges $Z=Z_B$, where ultra-compact trial functions lose their square-integrability, are estimated: $Z_B(1^1 S)\approx Z_B(2^1 S)\sim 0.905$ and $Z_B(1^3 S)\sim 0.902$. For both states the Majorana formula - the energy as a second degree polynomial in $Z$ - provides accurately 4-5 significant digits for $Z \leq 20$.