PNNL

Abstract

New correlation consistent-like basis sets have been developed for the post-d group 13 – 15 elements (Ga – As, In – Sb, Tl – Bi) employing accurate, small-core relativistic pseudopotentials. The resulting basis sets, which are denoted cc-pVnZ-PP, are appropriate for valence electron correlation and range in size from (8s7p7d)/[4s3p2d] for the cc-pVDZ-PP to (16s13p12d3f2g1h)/[7s7p5d3f2g1h] for the cc pV5Z-PP sets. Benchmark calculations on selected diatomic molecules (As2, Sb2, Bi2, AsN, SbN, BiN, GeO, SnO, PbO, GaCl, InCl, TlCl, GaH, InH, and TlH) are reported using these new basis sets at the coupled cluster level of theory. Much like their all-electron counterparts, the cc pVnZ-PP basis sets yield systematic convergence of total energies and spectroscopic constants. In several cases all-electron benchmark calculations were also carried out for comparison. The results from the pseudopotential and all-electron calculations were nearly identical when scalar relativity was accurately included in the all-electron work. Diffuse-augmented basis sets, aug-cc-pVnZ-PP, have also been developed and have been used in calculations of the atomic electron affinities.