All-electron basis sets for H to Xe specific for ZORA calculations: Applications in atoms and molecules

A segmented basis set of quadruple zeta valence quality plus polarization functions (QZP) for H through Xe was developed to be used in conjunction with the ZORA Hamiltonian. This set was augmented with diffuse functions to describe electrons farther away from the nuclei adequately. Using the ZORA-CCSD(T)/QZP-ZORA theoretical model, atomic ionization energies and bond lengths, harmonic vibrational frequencies, and atomization energies of some molecules were calculated. The addition of core-valence corrections has been shown to improve the agreement between theoretical and experimental results for molecular properties. For atomization energies, a similar observation emerges when considering spin-orbit couplings. With the augmented QZP-ZORA set, static mean dipole polarizabilities of a set of atoms were calculated and compared with previously published recommended and experimental values. Performance evaluations of the ZORA and Douglas–Kroll–Hess Hamiltonians were made for each property studied.