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

TL;DR

This paper explores how relativistic and electron correlation effects interact non-linearly, affecting atomic ionization energies in heavy atoms, and emphasizes the need for simultaneous treatment of both effects for accurate predictions.

Contribution

It demonstrates that relativistic and correlation effects on ionization energy are non-additive and interact in complex ways, challenging the assumption of their independence in heavy atoms.

Findings

Relativistic and correlation effects can enhance or cancel each other.

The order of adding effects influences the computed ionization energy.

Non-linearity indicates the need for combined treatment in calculations.

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.