Formation of HNC and HCN isomers in molecular plasmas revealed by frequency comb and quantum cascade laser spectroscopy

Abstract

Hydrogen cyanide (HCN) is a well-known product in combustion, astrophysical, and plasma environments, but its isomer, hydrogen isocyanide (HNC), remains unexplored in molecular plasmas. Here, we report on the detection and quantification of both HNC and HCN isomers in low-temperature plasmas generated from N₂/H₂/CH₄ mixtures using quantum cascade laser and frequency comb absorption spectroscopy. The identification of HNC is confirmed by comparison with molecular spectroscopic databases. The observed [HNC]/[HCN] abundance ratio of ∼10⁻⁴ is far lower than reported values in interstellar media, where ratios can reach unity. We attribute this stark difference to fundamentally different kinetics, dominated by an interplay between formation of vibrationally ‘hot’ intermediates (HCN* and HNC*) and their subsequent stabilization and destruction. This mechanism contrasts with cold interstellar environments, where dissociative recombination reactions dominate and the formed HNC persists and accumulates over astrochemical timescales. Our results highlight the overlooked role of HNC in plasma chemistry containing carbon, nitrogen and hydrogen, with implications for plasma-assisted HCN synthesis and nitrogen-carbon plasma processes in surface modification and material treatments.