Methanimine as a sink in the HCN and HNC solid state hydrogenation network

Abstract

We aim to provide a systematic and quantitative description of the hydrogenation network connecting HCN and HNC to methylamine on interstellar water ices, while identifying dominant pathways and bottlenecks. To this end, we performed a comprehensive quantum-chemical investigation of H-addition, H-abstraction, reactions with H2, and water-assisted H-transfer isomerization, covering intermediates linking HCN and HNC to CH3NH2. Calculations were carried out on amorphous solid water clusters of 14 molecules. Using benchmarked density functional theory, we derived activation barriers, elucidated mechanisms, and determined the binding energy distribution of H2CN and CNH2, also assessing deuterium substitution effects. H-addition reactions generally involve activation barriers, except for radical species. Considering both barrier heights and tunneling crossover temperatures, the most favorable sequence originates from HNC rather than HCN. The network evolves toward methanimine (H2CNH), the central species, or the singlet carbene HC:NH2, from which further hydrogenation leads to methylamine. Along these paths, several reactions are barrierless, while some H-abstraction processes compete with addition. Reactions involving H2 are uncommon, as most are endoergic. Deuterium substitution weakly affects classical barriers but significantly influences tunneling efficiencies. Our results support efficient formation of methanimine and methylamine from HNC on cold interstellar ices, with methanimine acting as a chemical sink, whereas HCN is less reactive and more likely to persist. These findings provide quantitative constraints for astrochemical models.