Potentials of the D10u+(61S0) and F31u(63P2) electronic Rydberg states of Cd2 from ab initio calculations and LIF excitation spectra

The method of supersonic free-jet expansion beam combined with techniques of laser spectroscopy was used in an investigation of vibronic and isotopic structures in the D10u+(61S0) and F31u(63P2) electronic energy Rydberg states of Cd2. Laser induced fluorescence excitation spectra recorded using the D10u+←X10g+(51S0) and F31u←X10g+ transitions in the region of 206-218 nm provided spectroscopic characteristics of the excited states and allowed constructing of their intratomic potentials. Isotopic structures recorded in the (υ′,υ″) bands of the D10u+←X10g+ transition were used in determination of the D10u+-state vibrational characteristics (ωe, ωexe) and υ′-assignment. The ν_0,0 recorded directly in the F31u←X10g+ transition enabled determination of the bottom of the F31u-state potential well. Valence ab initio calculations of Cd2 interatomic potentials were performed with relativistic and spin-orbit effects taken into account. The experimental results were compared with results of the ab initio calculations. A free-jet expansion of Cd2 as a source of entangled atoms for a test of Bell’s inequality was analyzed.