Hartree–Fock exchange fitting basis sets for H to Rn †

Abstract

For elements H to Rn (except Lanthanides), a series of auxiliary basis sets fitting exchange and also Coulomb potentials in Hartree-Fock treatments (RI-JK-HF) is presented. A large set of small molecules representing nearly each element in all its common oxidation states was used to assess the quality of these auxiliary bases. For orbital basis sets of triple zeta valence and quadruple zeta valence quality, errors in total energies arising from the RI-JK approximation are below approximately 1 meV per atom in molecular compounds. Accuracy of RI-JK-approximated HF wave functions is sufficient for being used for post-HF treatments like Møller-Plesset perturbation theory, MP2. Compared to nonapproximated treatments, RI-JK-HF leads to large computational savings for quadruple zeta valence orbital bases and, in case of small to midsize systems, to significant savings for triple zeta valence bases.