Theoretical study of the excited states of the Kr*2 excimer: Potential curves including a b i n i t i o spin–orbit coupling

The potential energy curves for all the adiabatic Ω states dissociating into Kr+Kr, Kr+Kr*(5s,5s′), Kr+Kr*(5p), and some higher states are calculated using multireference perturbative CI algorithms (CIPSI/CIPSO) with relativistic averaged and spin–orbit core pseudopotentials. A partially diabatic representation of the potential curves rationalizes the complex features of the adiabatic states induced by numerous avoided crossings. A systematic comparison is carried out with extensive experimental data, including absorption from the ground state, fluorescence data, and transient absorption spectroscopy.