High resolution overtone spectroscopy of HNC(+) and HCN().

Rotationally resolved spectra of the and molecular ions have been recorded in the spectral range between 6200 and 6800 cm using a cryogenic ion trap instrument. The rovibrational transitions were probed using two different action spectroscopy schemes, namely laser-induced reaction (LIR) and leak-out spectroscopy (LOS). Various vibrational bands of and were measured with high resolution for the first time. For , the XΣ(000)-(200) overtone band was recorded using LIR, while LOS was used to probe the XΠ(000)-(210)μ combination band and the XΠ(000)-AΣ(100) vibronic band of . Spectroscopic constants, band origins and radiative lifetimes for the observed states have been determined. The effective fit for the spectra revealed the presence of strong vibrational couplings leading to perturbations of the rovibrational levels of the excited states. The two action spectroscopy schemes are compared and their potential use to explore ion-molecule interactions is discussed.