High Resolution Overtone Spectroscopy of HNC$^+$ and HCN$^+$

TL;DR

This study reports high-resolution overtone spectra of HNC$^+$ and HCN$^+$ ions using cryogenic ion trap spectroscopy, revealing vibrational couplings and providing detailed spectroscopic constants for the first time.

Contribution

First high-resolution rovibrational spectra of HNC$^+$ and HCN$^+$ ions obtained using two action spectroscopy methods, with analysis of vibrational couplings and spectroscopic constants.

Findings

Measured vibrational bands of HNC$^+$ and HCN$^+$ for the first time.

Identified vibrational couplings causing perturbations in HCN$^+$ spectra.

Compared effectiveness of laser-induced reaction and leak-out spectroscopy.

Abstract

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 $\text{X}~^2\Sigma^+~(20^00)-(00^00)$ overtone band was recorded using LIR, while LOS was used to probe the $\text{X}~^2\Pi~(000)^1-(210)^0\mu$ combination band and the $\text{X}~^2\Pi~(000)^1-\text{A}~^2\Sigma^+~(10^00)$ 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.