Energy-consistent relativistic pseudopotentials for the 4d elements: Atomic and molecular applications

Abstract

Recently reported energy-consistent relativistic pseudopotentials have been used with series of matching correlation consistent basis sets in benchmark calculations of various atomic and molecular properties. The basis set convergence of the 4d metal electron affinities and 5 s2 →5 s0 excitation energies are reported at the CCSD(T) level of theory, and the effects of valence and 4s4p correlation are investigated. In addition the impact of correlating the low-lying 3d electrons was also studied in all-electron Douglas-Kroll-Hess (DKH) calculations, which also included the ionization potentials and 5 s2 →5 s1 excitation energies. For all four atomic properties, higher order coupled cluster calculations through CCSDTQ are reported. The final calculated values are generally all within 1 kcalmol of experiment. A notable exception is the ionization potential of Tc, the currently accepted experimental value of which is suggested to be too high by about 3 kcalmol. Molecular calculations are also reported for the low-lying electronic states of ZrO and RuF, as well as the ground electronic state of Pd2. The effects of spin-orbit coupling are investigated for these cases in pseudopotential calculations. Wherever possible, the pseudopotential results have been calibrated against DKH calculations with correlation consistent basis sets of triple-zeta quality. In all cases the calculated data for these species are in very good agreement with experiment. In particular, the correct electronic ground state for the RuF molecule ( 92 4) was obtained, which was made possible by utilizing systematic sequences of correlation consistent basis sets. © 2008 American Institute of Physics.