Dipole polarizabilities of the Group IIb atoms obtained from compact variational trial functions

Abstract

In order to optimize basis sets for future molecular calculations, the energies and dipole polarizabilities of ¹S, ³P, and ¹P states of Zn, Cd, and Hg have been determined from Hartree–Fock (HF) and multiconfiguration calculations. These utilize either empirically fitted pseudopotentials or ab initio effective core potentials (ECP). Our calculated polarizabilities for ground state atoms agree within 10% with recommended values so long as either the empirical pseudopotentials or the ECP based on relativistic HF calculations are used. Our calculations agree with the measured anisotropy of the polarizability of ³P₁ Hg, but disagree with measured values of the ³P₂ state anisotropy. Our calculated ³P₂ anisotropy is consistent with both the measured and calculated ³P₁ Hg anisotropy; the measured ³P₂ values are not. We find calculations based on nonrelativistic ECP to give incorrect polarizabilities.