Rovibrational investigation of a new high-lying 0_u ⁺ state of Cu₂ by using two-color resonant four-wave-mixing...

A highly excited electronic state of dicopper is observed and characterized for the first time. The [39.6]0_u ⁺-X¹Σ_g ⁺(0_g ⁺) system is measured at rotational resolution by using degenerate and two-color resonant four-wave-mixing, as well as laser induced fluorescence spectroscopy. Double-resonance experiments are performed by labeling selected rotational levels of the ground state by tuning the probe laser wavelength to transitions in the well-known (1-0) band of the B0_u ⁺-X¹Σ_g ⁺(0_g ⁺) electronic system. Spectra obtained by scans of the pump laser in the UV wavelength range were then assigned unambiguously by the stringent double-resonance selection rules. The absence of a Q-band suggests a parallel transition (ΔΩ = 0) and determines the term symbol of the state as 0_u ⁺ in Hund's case (c) notation. The equilibrium constants for ⁶³Cu₂ are T_e = 39 559.921(92) cm^-1, ω_e = 277.70(14) cm^-1, B_e = 0.104 942(66) cm^-1, and r_e = 2.2595(11) Å. These findings are supported by high-level ab initio calculations at the MRCI+Q level, which clearly identifies this state as resulting from a 4p ← 3d transition. In addition, three dark perturber states are found in the v = 1 and v = 2 vibrational levels of the new state. A deperturbation analysis characterizes the interaction and rationalizes the anomalous dips in the excitation spectrum of the [39.6]0_u ⁺-X¹Σ_g ⁺(0_g ⁺) system.