Relativistic segmented contraction basis sets with core-valence correlation effects for atoms 57La through 71Lu : Sapporo-DK-nZP sets (n = D, T, Q)

摘要

For the 15 lanthanide atoms 57La through 71Lu, we report Sapporo-DK-nZP sets (n = D, T, Q), which are natural extensions of the Sapporo-(DK)-nZP sets for lighter atoms and efficiently incorporate the correlation among electrons in the N through P shells as well as the relativistic effect. The present sets well describe the correlation among the 4s and 4p electrons, which are important in the excitation of 4f electrons. Atomic test calculations of 57La, 58Ce, 59Pr, and 60Nd at configuration interaction with the Davidson correction level of theory confirm high performance of the present basis sets. Molecular test calculations are carried out for 57LaF and 70YbF diatomics at the coupled cluster level of theory. The calculated spectroscopic constants approach smoothly to the experimental values as the quality of the basis set increases.