Quintet electronic states of N2

We use large scale ab initio calculations to investigate the valence and valence-Rydberg quintet states of N2, their transition moments and their spin-orbit couplings to the close lying triplet electronic states. In addition to the A′ ∑5g+ and the C″ Π5ui states already known, we identify two weakly bound states (2 ∑5g+ and 2 Π5u) at ∼95 300 and 106 200 cm−1 above N2(X ∑1g+,  v=0). The other quintets are viewed to be repulsive in nature. Our potentials and couplings are used later to derive a set of accurate spectroscopic data for these quintets, their spin-orbit constants, and to elucidate the quintet-triplet dynamics and the role of these newly identified quintets for the production of cold atomic nitrogen.