Interatomic potentials of metal dimers: probing agreement between experiment and advanced ab initio calculations for van der Waals dimer Cd2

Abstract

Abstract A critical review of experimental studies and ab initio calculations of the low-lying ungerade excited and ground state interatomic potentials of Cd2 van der Waals dimer is presented. Consistency as well as discrepancies between experimental results and ab initio calculations are probed. In order to obtain better agreement with existing experimental data, fill in gaps in current knowledge and provide a unifying framework, advanced all-electron ab initio calculations were performed and simulations of the reported spectra were executed. From simulations of laser-induced fluorescence excitation and dispersed emission spectra, analytical and/or point-wise representations of the (51P1), B11u(51P1), a31u(53P1), (53P1) and c31u(53P2) excited-, and the (51S0) ground-state Cd2 interatomic potentials were obtained. The comparison of the ab initio calculated potentials with results of the analyses allows to illustrate a current state-of-the-art of theory-and-experiment correspondence for such a demanding system. Results are presented in the context of an importance of the group 2 and group 12 metal dimer interatomic potentials especially, in ultra-cold physics and chemistry, and in fundamental tests of quantum mechanics.