Diffuse basis functions for explicitly correlated calculations on the heavy p-block: aug-cc-pVnZ-PP-F12 sets for Ga-Kr, In-Xe, and Tl-Rn.

Abstract

New aug-cc-pVnZ-PP-F12 basis sets (n = D, T, Q) for the heavy p-block elements, Ga-Kr, In-Xe, and Tl-Rn, have been developed by augmenting the cc-pVnZ-PP-F12 sets with additional higher angular momentum diffuse functions. These basis sets have been optimized for use in explicitly correlated F12 calculations, and matching auxiliary basis sets for density fitting of conventional and F12 integrals have also been developed. The new sets have been validated with benchmark CCSD(T)-F12b calculations of electron affinities, where an accelerated convergence to the complete basis set limit is evident. The effect of the additional diffuse functions on electron affinities is shown to be comparable to the effect of correlating the outer-core d electrons.