Shedding light on a dark state: the energetically lowest quintet state of C2

In this work we present a deperturbation study of the d?(3)Π(g), v=6 state of C(2) by double-resonant four-wave mixing spectroscopy. Accurate line positions of perturbed transitions are unambiguously assigned by intermediate level labeling. In addition, extra lines are accessible by taking advantage of the sensitivity and high dynamic range of the technique. These weak spectral features originate from nearby-lying dark states that gain transition strength through the perturbation process. The deperturbation analysis of the complex spectral region in the (6,5) and (6,4) bands of the Swan system (d(3)Π(g)-a?(3)Π(u)) unveils the presence of the energetically lowest high-spin state of C(2) in the vicinity of the d?(3)Π(g), v=6 state. The term energy curves of the three spin components of the d state cross the five terms of the 1?(5)Π(g) state at rotational quantum numbers N ≤ 11. The spectral complexity for transitions to the v = 6 level of d?(3)Π(g) state is further enhanced by an additional perturbation at N = 19 and 21 owing to the b?(3)Σ(g)(-), v=19 state. The spectroscopic characterization of both dark states is accessible by the measurement of 122 "window" levels. A global fit of the positions to a conventional Hamiltonian for a linear diatomic molecule yields accurate molecular constants for the quintet and triplet perturber states for the first time. In addition, parameters for the spin-orbit and L-uncoupling interaction between the electronic levels are determined. The detailed deperturbation study unravels major issues of the so-called high-pressure bands of C(2). The anomalous nonthermal emission initially observed by Fowler in 1910 Mon. Not. R. Astron. Soc. 70, 484 (1910)] and later observed in numerous experimental environments are rationalized by taking into account "gateway" states, i.e., rotational levels of the d?(3)Π(g), v=6 state that exhibit significant (5)Π(g) character through which all population flows from one electronic state to the other.