Quasirelativistic valence ab initio calculation of the potential-energy curves for Cd-rare gas atom pairs

The results of large-scale valence ab initio calculations of the potential- energy curves for the ground states and several excited states of Cd-rare g as (RG) van der Waals molecules are reported. in the calculations. Cd20+ an d RG(8+) cores are simulated by energy-consistent pseudopotentials, which a lso account for scalar-relativistic effects and spin-orbit interaction with in the valence shell. The potential energies of the Cd-RG species in the La mbdaS coupling scheme have been evaluated by means of ab initio complete-ac tive-space multiconfiguration self-consistent-field (CASSCF)/CAS multirefer ence second-order perturbation theory (CASPT2) calculations with a total 28 valence electrons, but the spin-orbit matrix has been computed in a reduce d configuration interaction space restricted to the CASSCF level, Finally, the Omega potential curves are obtained by diagonalization of the modified spin-orbit matrix (its diagonal elements before diagonalization substituted by the corresponding CASPT2 eigenenergies). The calculated potential curve s, especially the spectroscopic parameters derived for the ground states an d several excited states of the Cd-RG species are presented and discussed i n the context of available experimental data. The theoretical results exhib it very good agreement with experiment.