Gaussian basis set of triple zeta valence quality for the atoms from K to Kr: Application in DFT and CCSD(T) calculations of molecular properties

Abstract

A contracted basis set of triple zeta (TZ) valence quality for the atoms from K to Kr was constructed from fully-optimized Gaussian basis sets generated in this work. Gaussian polarization functions (d, f, and g symmetries), which were optimized at the second-order Mφller–Plesset level, were added to the TZ set. This extends earlier work on segmented contracted TZ basis set for atoms H-Ar. This set along with the BP86 non-hybrid and B3LYP hybrid functionals were used to calculate geometric parameters, dissociation energy, harmonic vibrational frequency, and electric dipole moment of a sample of molecules and, then, comparison with results obtained with other basis sets and with experimental data reported in the literature is done. CCSD(T) atomic excitation energies and bond lengths, dissociation energies, and harmonic vibrational frequencies of some diatomics were also evaluated. Using density functional theory and gauge-including atomic orbitals, 57Fe and 77Se nuclear magnetic resonance chemical shifts in Fe(C5H5)2, H2Se, (CH3)SeH, CSe2, SeCO, H2CSe, and SeF6 were calculated. Comparison with theoretical and experimental values previously published in the literature was done. It is verified that in general these results give good agreement with experimental and benchmark values.