Relativistic and Electron Correlation Effects in Static Dipole Polarizabilities for Main-Group Elements

TL;DR

This paper calculates atomic dipole polarizabilities for main-group elements using advanced relativistic and correlation methods, revealing how different relativistic effects and electron correlations influence these properties across the periodic table.

Contribution

It provides a comprehensive dataset and systematic analysis of relativistic and electron correlation effects on atomic polarizabilities, enhancing understanding of these influences.

Findings

Scalar-relativistic effects dominate for Groups 1--2.

Spin-orbit coupling significantly affects heavier elements in Groups 13--18.

Electron correlation impacts polarizabilities notably for Groups 1--2 and 13--14.

Abstract

In this study, I compute the static dipole polarizability of main-group elements using the finite-field method combined with relativistic coupled-cluster and configuration interaction simulations. The computational results closely align with the values recommended in the 2018 table of static dipole polarizabilities of neutral elements [Mol. Phys. 117, 1200 (2019)]. Additionally, I investigate the influence of relativistic effects and electron correlation on atomic dipole polarizabilities. Specifically, three types of relativistic effects impacting dipole polarizabilities are studied: scalar-relativistic, spin-orbit coupling, and fully relativistic Dirac-Coulomb effects. The results indicate that scalar-relativistic effects are predominant for atoms in Groups 1--2, with minimal influence from spin-orbit coupling effects. Conversely, for elements in Groups 13--18, scalar-relativistic effects are less significant, while spin-orbit coupling significantly affects elements starting from the fourth row in Groups 13--14 and from the fifth row in Groups 15--18. In each category of relativistic effects, the impact of electron correlation is evaluated. The results show that electron correlation significantly influences dipole polarizability calculations, particularly for Groups 1--2 and 13--14 atoms, but is less significant for Groups 15--18 atoms. This study provides a comprehensive and consistent dataset of dipole polarizabilities and contributes to a systematic understanding of the roles of relativistic and electron correlation effects in atomic dipole polarizabilities, serving as a valuable reference for future research.