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arxiv: 2606.00814 · v1 · pith:XXOTQQI4new · submitted 2026-05-30 · ⚛️ physics.atom-ph

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

classification ⚛️ physics.atom-ph
keywords quantumdefectstatesenergyionizationnonrelativisticrydbergtheory
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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 (QED) 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 $1snp\;^1P_1$ and $^3P_c$ (centroid) states up to $n=102$ with accuracies better than $\pm$1 kHz. The calculated ionization energies are combined with 28 measured transition frequencies to obtain values for the ionization energy of the $1s2s\;^3S_1$ state. The final result of 1152 842 742.705(16) MHz differs from theory by $0.474\pm 0.052$ MHz, and provides a strong confirmation of the 9$\sigma$ 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 $1/n^2$ in lowest order. The nonrelativistic part provides a theoretical justification for the effective reduced-mass Rydberg $R_M^{(+)}$ based on the phenomenological model of a Rydberg electron scattering from a He$^+$ core. The Ritz expansion for the nonrelativistic energy is verified to an unprecedented 20-figure accuracy.

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