Relativistic and electron-correlation effects in static dipole polarizabilities for group 12 elements

TL;DR

This paper presents highly accurate calculations of static dipole polarizabilities for group 12 elements, systematically analyzing relativistic and electron-correlation effects using advanced quantum chemistry methods.

Contribution

It provides the first comprehensive relativistic coupled-cluster calculations of polarizabilities for group 12 elements, including uncertainties and detailed relativistic effects analysis.

Findings

Relativistic effects significantly influence polarizabilities, with scalar-relativistic effects dominating.

Spin-orbit coupling contributions are negligible for these elements.

Results agree well with previous data, reducing uncertainties for Cd and Cn.

Abstract

In this study, we report a comprehensive calculation of static dipole polarizabilities for group 12 elements using the finite-field approach in conjunction with the relativistic coupled-cluster method, including single, double, and perturbative triple excitations. Relativistic effects are systematically explored, encompassing scalar-relativistic, spin-orbit coupling (SOC), and full Dirac-Coulomb contributions. The recommended polarizability values, with uncertainties, are $37.95 \pm 0.77$ a.u. for Zn, $45.68 \pm 1.21$ a.u. for Cd, $34.04 \pm 0.68$ a.u. for Hg, and $27.92 \pm 0.28$ a.u. for Cn. These results are in excellent agreement with the 2018 compilation of static dipole polarizabilities [Mol. Phys. \textbf{117}, 1200 (2019)] and reduce uncertainties for Cd and Cn. Our analysis demonstrates that scalar-relativistic effects dominate the relativistic corrections, with SOC contributions found to be negligible. The role of electron correlation is examined across all relativistic regimes, highlighting its critical importance in achieving accurate polarizability predictions.