Theory for the Rydberg states of helium: Comparison with experiment for the $1s24p\;^1P_1$ state ($n=24$)

TL;DR

This paper develops a highly precise theoretical method using a triple basis set in Hylleraas coordinates to accurately calculate Rydberg states of helium, achieving results that match experimental data and reveal discrepancies in previous theories.

Contribution

The paper introduces a novel computational approach with a triple basis set in Hylleraas coordinates to improve accuracy of Rydberg state calculations for helium.

Findings

Achieved 23 significant figures in nonrelativistic energies.

Calculated ionization energy matches experimental data within 1 kHz.

Confirmed a significant discrepancy between theory and experiment in helium's triplet spectrum.

Abstract

Recent measurements of the ionization energies of the Rydberg $^1P$ states of helium for principal quantum number $n = 24$ and higher present a new challenge to theoretical atomic physics. A long-standing obstacle to high precision atomic theory for three-body systems is a rapid loss of accuracy for variational calculations with increasing principal quantum number $n$. We show that this problem can be overcome with the use of a ``triple" basis set in Hylleraas coordinates. Nonrelativistic energies accurate to 23 significant figures are obtained with basis sets of relatively modest size (6744 terms). Relativistic and quantum electrodynamic effects are calculated, including an estimate of terms of order $m\alpha^6$ from a $1/n^3$ extrapolation, resulting in an estimated accuracy of $\pm$1 kHz. The calculated ionization energy of 5704 980.348(1) MHz is in excellent agreement with the experimental value 5704 980.312(95) MHz. These results establish the ionization energy of the $1s24p\;^1P_1$ state as an absolute point of reference for transitions to lower-lying states, and they confirm an $11\sigma$ disagreement between theory and experiment in the triplet spectrum of helium. Results are also given for the $1s24p\;^3P_J$ states in agreement with a recent experiment on the triplet Rydberg series, thereby confirming a discrepancy of of $0.468 \pm 0.055$ MHz for the ionization energy of the $1s2s\;^3S_1$ state.