Gaussian basis sets of triple and quadruple zeta valence quality for correlated wave functions

Abstract

Contracted basis sets of triple and quadruple zeta (TZ and QZ, respectively) valence quality for the atoms from H to Ar are presented. They have been determined from fully-optimized basis sets of primitive Gaussian-type functions generated in atomic Hartree–Fock (HF) calculations. Sets of Gaussian polarization functions optimized at the Møller–Plesset second-order (MP2) level were added to the TZ and QZ basis sets. This extends earlier work on segmented contracted double zeta valence basis sets. The performance of the basis sets are assessed in molecular HF and MP2 calculations for a sample of diatomic molecules by a comparison of energies, dissociation energies, and dipole moments with results obtained numerically or using basis sets reported in the literature. By fitting the directly calculated values through two extrapolation schemes, estimates of the complete basis set limit for second order correlation energy have been obtained. In addition, results for MP2-R12/A calculations to establish the basis set convergence for the standard calculations are also presented.