Theory for the Rydberg states of helium: Quantum defect extensions and comparison with experiment up to for the singlet and triplet states
Phys. Rev. A 114, 022827 – Published 26 August, 2026
DOI: https://doi.org/10.1103/jzjp-k8yc
Abstract
High-precision variational calculations for helium in Hylleraas coordinates are used to obtain a combination of quantum defect expansions for the nonrelativistic energy and expansions for the relativistic and quantum electrodynamic corrections. The extrapolations based on direct calculations for the singlet and triplet states up to principal quantum number provide ionization energies of the and (centroid) states up to with accuracies better than kHz. The calculated ionization energies are combined with 28 measured transition frequencies to obtain values for the ionization energy of the state. The final result of 1 152 842 742.705(16) MHz differs from theory by MHz, and provides a strong confirmation of the disagreement between theory and experiment obtained previously by quantum defect extrapolation of experimental data to the series limit. An analysis of the quantum defect method is presented, and second-order mass polarization (recoil) terms are identified that vary as in lowest order. The nonrelativistic part provides a theoretical justification for the effective reduced-mass Rydberg based on the phenomenological model of a Rydberg electron scattering from a core. The Ritz expansion for the nonrelativistic energy is verified to 20-figure accuracy.