A comparative study of correlation and relativistic effects on atomic ionization energy

IF 4.6 2区物理与天体物理 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY

Results in Physics Pub Date : 2026-02-01 Epub Date: 2026-01-19 DOI:10.1016/j.rinp.2026.108588

Mohamed Kahil , Fatima Fakih , Nabil Joudieh , Nidal Chamoun

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引用次数: 0

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

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原子电离能的相关效应与相对论效应之比较研究

本文研究了相对论效应和电子相关效应对重原子（Au ~ Rn, Z = 79 ~ 86）第一电离能的相互作用。我们进行了两项互补分析：(1)比较在har树- fock （HF）和耦合簇CCSD(T)水平上计算的相对论校正，以评估相关性如何影响相对论校正的大小；(2)比较在非相对论和相对论框架下计算的相关校正，以确定相对论如何影响相关校正的大小。我们的研究结果揭示了这两种效应之间惊人的非线性关系。具体地说，相对论和相关性对电离能的综合影响并不等于它们各自贡献的总和。这种非加性表明相对论效应和相关效应不是相互独立的；它们以依赖于原子系统的复杂方式相互作用。我们发现，对于某些原子，这两种效应相互增强，而对于另一些原子，它们部分抵消。此外，人们可能添加“分离”效应的顺序也很重要，因为将“纯”相对论效应添加到剩余结果（包括相关性）将得到与将“纯”相关效应添加到剩余结果（包括相关性）时不同的结果。这些发现表明相对论和相关效应本质上是非加性的，反映了量子多体问题的非线性。因此，对重元素系统中电离能的精确计算预测需要同时处理这两种效应，而不是将它们作为独立的贡献来处理

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Results in Physics MATERIALS SCIENCE, MULTIDISCIPLINARYPHYSIC-PHYSICS, MULTIDISCIPLINARY

CiteScore

8.70

自引率

9.40%

发文量

754

审稿时长

50 days

期刊介绍： Results in Physics is an open access journal offering authors the opportunity to publish in all fundamental and interdisciplinary areas of physics, materials science, and applied physics. Papers of a theoretical, computational, and experimental nature are all welcome. Results in Physics accepts papers that are scientifically sound, technically correct and provide valuable new knowledge to the physics community. Topics such as three-dimensional flow and magnetohydrodynamics are not within the scope of Results in Physics. Results in Physics welcomes three types of papers: 1. Full research papers 2. Microarticles: very short papers, no longer than two pages. They may consist of a single, but well-described piece of information, such as: - Data and/or a plot plus a description - Description of a new method or instrumentation - Negative results - Concept or design study 3. Letters to the Editor: Letters discussing a recent article published in Results in Physics are welcome. These are objective, constructive, or educational critiques of papers published in Results in Physics. Accepted letters will be sent to the author of the original paper for a response. Each letter and response is published together. Letters should be received within 8 weeks of the article''s publication. They should not exceed 750 words of text and 10 references.