Perturbed Coupled-Cluster theory to calculate dipole polarizabilities of closed shell systems: Application to Ar, Kr, Xe and Rn

TL;DR

This paper employs perturbed relativistic coupled-cluster theory to accurately compute the electric dipole polarizabilities of noble gas atoms, incorporating nonlinear terms and relativistic effects, with detailed analysis of Breit interaction contributions.

Contribution

The study introduces a detailed formulation of nonlinear terms in PRCC theory and applies it to noble gases, highlighting relativistic and Breit interaction effects on polarizability calculations.

Findings

Breit interaction contributes up to 0.1% for Rn.

Relativistic contraction of outer p_{1/2} orbitals observed.

PRCC theory effectively captures nonlinear and relativistic effects.

Abstract

We use perturbed relativistic coupled-cluster (PRCC) theory to calculate the electric dipole polarizability of noble gas atoms Ar, Kr, Xe and Rn. We also provide a detailed description of the nonlinear terms in the PRCC theory and consider the Dirac-Coulomb-Breit atomic Hamiltonian for the calculations. We find that the largest contribution from Breit interaction to the electric dipole polarizability is 0.1%, in the case of Rn. As we go from Ar to Rn, based on the pattern in the random phase approximation effects, the contraction of the outermost $p_{1/2}$ due to relativistic corrections is discernible without any ambiguity.