Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn.

Abstract

A relativistic coupled-cluster version of the Feller-Peterson-Dixon composite method has been used to accurately calculate the first ionization potentials (IPs) and electron affinities (EAs) of the post-d, p-block elements Ga-Rn. Complete basis set extrapolations including outer-core correlation at the CCSD(T) level of theory were combined with contributions from higher order electron correlation up to CCSDTQ, quantum electrodynamic effects (Lamb shift), and spin-orbit (SO) coupling including the Gaunt contribution. Several methods for including SO were investigated, in which all involved the four-component (4c) Dirac-Coulomb (DC) Hamiltonian. The treatment of SO coupling was the contribution that limited the final accuracy of the present results. In the cases where 4c-DC-CCSD(T) could be reliably used for the SO contributions, the final composite IPs and EAs agreed with the available experimental values to within an unsigned average error of just 0.16 and 0.20 kcal/mol, respectively. In all cases, the final IPs and EAs were within 1 kcal/mol of the available experimental values, except for the EAs of the group 13 elements (Ga, In, and Tl), where the currently accepted experimental values appear to be too large by as much as 4 kcal/mol. The values predicted in this work, which have estimated uncertainties of ±0.5 kcal/mol, are 5.25 (Ga), 7.69 (In), and 7.39 (Tl) kcal/mol. For the EAs of Po and At, which do not have experimental values, the current calculations predict values of 34.2 and 55.8 kcal/mol with estimated uncertainties of ±0.6 and ±0.3 kcal/mol, respectively.