János Sarka

Rotationally resolved spectra of the HNC$^+$ and HCN$^+$ molecular ions have been recorded in the spectral range between 6200 and 6800 \rcm\ 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 HNC$^+$ and HCN$^+$ were measured with high resolution for the first time. For HNC$^+$, the $\text{X}~^2Σ^+~(20^00)-(00^00)$ overtone band was recorded using LIR, while LOS was used to probe the $\text{X}~^2Π~(000)^1-(210)^0μ$ combination band and the $\text{X}~^2Π~(000)^1-\text{A}~^2Σ^+~(10^00)$ vibronic band of HCN$^+$. Spectroscopic constants, band origins and radiative lifetimes for the observed states have been determined. The effective fit for the HCN$^+$ 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.

Spectra of vibrational overtone and combination bands from vibrational ground state of HCNH+ were measured using an action spectroscopy technique with active background suppression in a cryogenic 22 pole radio frequency ion trap apparatus. Spectroscopic constants for the upper vibrational levels of the transitions were determined with vibrational band origins being 6846.77981(90) $\text{cm}^{-1}$ ($2ν_1$ , NH stretch), 6640.47624(43) $\text{cm}^{-1}$ ($ν_1 + ν_2$), 6282.03578(63) $\text{cm}^{-1}$ ($2ν_2$, CH stretch), and 6588.4894(20) $\text{cm}^{-1}$ ($ν_2 + ν_3 + 2ν_5^0$). State of the art ab initio VCI calculations up to 10000 $\text{cm}^{-1}$ complement the experimental data.