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    Theory for the Rydberg states of helium: Quantum defect extensions and comparison with experiment up to n=102 for the singlet and triplet P states

    G. W. F. Drake1 and Aaron T. Bondy2

    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 1/n expansions for the relativistic and quantum electrodynamic corrections. The extrapolations based on direct calculations for the singlet and triplet P states up to principal quantum number n=35 provide ionization energies of the 1snpP11 and Pc3 (centroid) states up to n=102 with accuracies better than ±1 kHz. The calculated ionization energies are combined with 28 measured transition frequencies to obtain values for the ionization energy of the 1s2sS13 state. The final result of 1 152 842 742.705(16) MHz differs from theory by 0.474±0.052 MHz, and provides a strong confirmation of the 9σ 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 1/n2 in lowest order. The nonrelativistic part provides a theoretical justification for the effective reduced-mass Rydberg RM(+) based on the phenomenological model of a Rydberg electron scattering from a He+ core. The Ritz expansion for the nonrelativistic energy is verified to 20-figure accuracy.

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