Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy

TLDR

The paper presents Gaussian basis sets of quadruple‑zeta valence quality for Rb–Rn and split‑valence and triple‑zeta valence quality for H–Rn. The authors derived the new bases by partially modifying existing sets and evaluated them on a large test set of over 300 molecules spanning nearly all elements (except lanthanides) in common oxidation states, examining atomization energies, dipole moments and structural parameters at Hartree–Fock, DFT and MP2 levels. The study recommends the most suitable basis set for each level of theory and desired accuracy.

Abstract

Gaussian basis sets of quadruple zeta valence quality for Rb–Rn are presented, as well as bases of split valence and triple zeta valence quality for H–Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements—except lanthanides—in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree–Fock, density functional theory and correlated methods, for which we had chosen Møller–Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.