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High-resolution electronic spectroscopy of a nonlinear carbon chain radical C6H4+

A high-resolution gas-phase spectrum of a molecular absorption band around 604 nm is assigned as due to an electronic transition of a nonlinear C6H4+ planar species starting from its 2A″ electronic ground state. The spectrum is observed in direct absorption by cavity ringdown spectroscopy through a supersonic planar discharge through a mixture of acetylene in helium. The spectrum has a clear rotational and K-type structure. This allows an accurate determination of the B and C rotational constants and an estimate for the A rotational constant in ground and electronically excited states. The resolved spectrum of the fully deuterated species C6D4+ has been obtained as well. The results are compared both to the outcome of ab initio geometry optimizations and low-resolution absorption spectra in 6 K neon matrices obtained after mass-selective deposition.