Infrared study of ion-irradiated N2-dominated ices relevant to Triton and Pluto: formation of HCN and HNC

Infrared spectra and radiation chemical behavior of N₂-dominated ices relevant to the surfaces of Triton and Pluto are presented. This is the first systematic IR study of proton-irradiated N₂-rich ices containing CH₄ and CO. Experiments at 12 K show that HCN, HNC, and diazomethane (CH₂N₂) form in the solid phase, along with several radicals. NH₃ is also identified in irradiated N₂ + CH₄ and N₂ + CH₄ + CO. We show that HCN and HNC are made in irradiated binary ice mixtures having initial N₂/CH₄ ratios from 100 to 4, and in three-component mixtures have an initial N₂/(CH₄ + CO) ratio of 50. HCN and HNC are not detected in N₂-dominated ices when CH₄ is replaced with C₂H₆, C₂H₂, or CH₃OH.The intrinsic band strengths of HCN and HNC are measured and used to calculate G(HCN) and G(HNC) in irradiated N₂ + CH₄ and N₂ + CH₄ + CO ices. In addition, the HNC/HCN ratio is calculated to be ∼1 in both icy mixtures. These radiolysis results reveal, for the first time, solid-phase synthesis of both HCN and HNC in N₂-rich ices containing CH₄.We examine the evolution of spectral features due to acid-base reactions (acids such as HCN, HNC, and HNCO and a base, NH₃) triggered by warming irradiated ices from 12 K to 30-35 K. We identify anions (OCN⁻, CN⁻, and N3−) in ices warmed to 35 K. These ions are expected to form and survive on the surfaces of Triton and Pluto. Our results have astrobiological implications since many of these products (HCN, HNC, HNCO, NH₃, NH₄OCN, and NH₄CN) are involved in the syntheses of biomolecules such as amino acids and polypeptides.