Relativistic dsp-model core potentials for main group elements in the fourth, fifth and sixth row and their applications

Abstract

We have developed advanced relativistic model core potentials ( dsp-MCPs) for the fourth (Ga–Kr), fifth (In–Xe) and sixth-row (Tl–Rn) main-group elements, where the outermost core ( n−1) d electrons were treated explicitly as well as the ns and np valence electrons. The remaining core electrons were replaced by dsp-MCPs. The major relativistic effects were incorporated into the dsp-MCPs at the level of Cowan and Griffin's quasi-relativistic Hartree–Fock method. We applied dsp-MCPs to calculate spectroscopic constants for the ground states of the rare-gas diatomic molecules Kr 2 and Xe 2. The results obtained by coupled pair approximation using atomic natural orbital (ANO) basis sets, in which the correlation of inner ( n−1) d electrons was included as well as those of the valence ns and np electrons, give excellent agreement with experimental values.