We elucidate mechanisms of electron-induced radiolysis in cosmic (interstellar, planetary, and cometary) ice analogs of ammonia (NH3), likely the most abundant nitrogen-containing compound in the interstellar medium (ISM). Astrochemical processes were simulated under ultrahigh vacuum conditions by high-energy (1 keV) and low-energy (7 eV) electron-irradiation of nanoscale thin films of ammonia deposited on cryogenically cooled metal substrates. Irradiated films were analyzed by temperature-programmed desorption (TPD). Experiments with ammonia isotopologues provide convincing evidence for the electron-induced formation of hydrazine (N2H4) and diazene (N2H2) from condensed NH3. To understand the dynamics of ammonia radiolysis, the dependence of hydrazine and diazene yields on incident electron energy, electron flux, electron fluence, film thickness, and ice temperature were investigated. Radiolysis yield measurements versus (1) irradiation time and (2) film thickness are semiquantitatively consistent with a reaction mechanism that involves a bimolecular step for the formation of hydrazine and diazene from the dimerization of amidogen (NH2) and imine (NH) radicals, respectively. The apparent decrease in radiolysis yield of hydrazine and diazene with decreasing electron flux at constant fluence may be due to the competing desorption of these radicals at 90 K under low incident electron flux conditions. The production of hydrazine at electron energies as low as 7 eV and an ice temperature of 22 K is consistent with condensed phase radiolysis being mediated by low-energy secondary electrons produced by the interaction of high-energy radiation with matter. These results provide a basis from which we can begin to understand the mechanisms by which ammonia can form more complex species in cosmic ices.
Shulenberger, K. E.; Zhu, J.; Tran, K.; Abdullahi, S.; Belvin, C.; Lukens, J.; Peeler, Z.; Mullikin, E.; Cumberbatch, H.; Huang, J.; Regovich, K.; Zhou A.; Heller, L.; Markovic, M.; Gates, L.; Buffo, C.; Tano-Menka, R.; Arumainayagam, C.R.; Böhler E., Swiderek, P.; Esmaili, S.; Bass, A.D.; Huels M., and Sanche, L., “Electron-Induced Radiolysis of Astrochemically Relevant Ammonia Ices.,” ACS Earth and Space Chemistry 2019, 3, 800−810; DOI:10.1021/acsearthspacechem.8b00169.