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arXiv:2602.05659

A Comparative Study of Correlation and Relativistic Effects on Atomic Ionization Energy

Mohamed Kahil, Fatima Fakih, Nabil Joudieh, Nidal Chamoun

physics.atom-phquant-phSubmitted Feb 5, 2026• Announced Feb 6, 2026
arXivHTMLPDF

Abstract

This study investigates the interplay between relativistic effects and electron correlation effects on the first ionization energies of heavy atoms (Au through Rn, Z = 79-86). We perform two complementary analyses: (1) comparing relativistic corrections computed at both the Hartree-Fock (HF) and coupled cluster CCSD(T) levels to assess how correlation influences the magnitude of relativistic corrections, and (2) comparing correlation corrections computed within both non-relativistic and relativistic frameworks to determine how relativity influences the magnitude of correlation corrections. Our results reveal a striking non-linear relationship between these two effects. Specifically, the combined effect of relativity and correlation on ionization energy does not equal the sum of their individual contributions. This non-additivity indicates that relativistic and correlation effects are not independent; they interact in complex ways that depend on the atomic system. We find that for some atoms, the two effects enhance each other, while for others they partially cancel. Moreover, the order in which one may add "separate" effects also counts, in that adding "pure" relativistic effects to the remaining outcome (including correlation) would give a different result than when adding "pure" correlation effects to the remaining outcome (including relativity). These findings demonstrate that relativistic and correlation effects are inherently non-additive, reflecting the non-linearity of the quantum many-body problem. Accurate computational predictions of ionization energies in heavy-element systems thus require simultaneous treatment of both effects rather than treating them as independent contributions.

Journal reference
Results in Physics 81 (2026) 108588
DOI
10.1016/j.rinp.2026.108588
Comments
12 pages, 2 figures, 3 Tables

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These findings demonstrate that relativistic and correlation effects are inherently non-additive, reflecting the non-linearity of the quantum many-body problem. Accurate computational predictions of ionization energies in heavy-element systems thus require simultaneous treatment of both effects rather than treating them as independent contributions.
Investigating Role of Electron Correlation Effects via Triple Excitations for Precise Evaluation of Energies and Hyperfine Structure Constants in 23^{23}23Na
Accurate determination of hyperfine structure constants in atomic systems provides important insight into the interplay of electron correlation and relativistic effects in the nuclear region. Although sodium (Na) is a relatively light atom, previous all-order relativistic many-body calculations of the magnetic dipole hyperfine constants for the low-lying states of 23^{23}23Na show noticeable discrepancies with experiment. To address this, we calculate the ionization potentials and hyperfine structure constants of 23^{23}23Na using relativistic coupled-cluster theory with explicit inclusion of triple excitations. We further incorporate corrections from the Breit interaction, quantum electrodynamics, and the Bohr-Weisskopf (BW) effect. Results from lower-order methods are also presented to assess the importance of different physical contributions across states. Our calculations demonstrate that contributions from the lower-order relativistic and BW effects play almost similar roles with the electron correlation effects, including triple excitations, and are essential for reconciling theoretical predictions with experimental observations. This study can also serve as a useful guide for understanding the role of triples in heavier alkali systems.
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We present relativistic many-body calculations of the fine-structure splittings of the n2Fn\phantom{\rule{0.16em}{0ex}}{}^{2}Fn2F Rydberg states of Rb (n=4(n=4(n=4--16) using both order-by-order relativistic many-body perturbation theory (RMBPT), up to a subset of fourth-order corrections, and relativistic equation-of-motion coupled-cluster methods, including singles, doubles, and an approximate treatment of valence triples. Good overall agreement is found with the measurements of Brandenberger et al. [Phys. Rev. A 65, 042510 (2002); Phys. Rev. A 81, 032515 (2010)] to better than the 1% level, which is our expected level of theoretical uncertainty due to omitted higher-order correlation effects. It is shown that the RMBPT of the fine-structure splittings is complex and slowly convergent, and that relativistic effects are enhanced compared with the RMBPT of the ionization energy of the 2F^{2}\mathrm{F}2F states. We also analyze smaller field-theoretic contributions to the fine-structure splittings from retardation and the radiative self-energy and vacuum polarization, finding them to enter at the 0.1% level.
Abstract Using the singles and doubles approximated relativistic coupled-cluster method, we calculate hyperfine-structure constant A and B of 24 low-lying states of La 2+ . The results of the lowest four states 5 d 3/2,5/2 and 4 f 5/2,7/2 are compared with recently measured values (Olmschenk et al 2017 Phys. Rev. A 96 032502). Reasonable agreement is found for hyperfine-structure constant A of 5 d 3/2 and 4 f 5/2,7/2 states, but the hyperfine-structure constant A of 5 d 5/2 and the hyperfine-structure constant B have a large deviation. To understand the role of the electron correlation effect, the intermediate results from lower-order many-body perturbation-theory and the linear version of coupled-cluster with single and double approximation are also presented. In the framework of coupled-cluster theory, the contribution trends from individual correlation effects are also investigated.
We experimentally compute relativistic and correlation effects in the atomic properties by using a superconducting qubit processor. Specifically, we compute the relativistic ground-state energies and magnetic-dipole hyperfine structure constants for four Li-like atomic systems ranging from very light to moderately heavy to very heavy in terms of nuclear charge. A symmetry-conserving Bravyi-Kitaev transformation is used to reduce the original six-qubit problem to a four-qubit problem, which is experimentally contrived by reducing the hardware requirement by employing a virtual two-qubit gate. It enables the simulation of four-qubit circuits using two physical qubits with additional circuit evaluations. The ground-state wave functions, required for computing atomic properties, are obtained by using quantum state tomography. Our results show that the averaged relative errors for the ground-state energies are ≈ 0.3 ± 1 % . However, for the hyperfine structure constants, the mean values of the relative errors are less than 15 % , with their estimated upper bound of relative errors of ≈ ± 10 % (with the exception of 7.2 ± 47 % for neutral Li 7 ). Notably, our results for the hyperfine structure constants exhibit higher sensitivity to errors as compared to energies; a trend which we also confirm through additional numerical simulations. Published by the American Physical Society 2024