Gaseous reaction mechanism between two H2CN radicals

Abstract

The self-recombination of the methylene amidogen radical (H₂CN) is known to be fast and should play an important role in determining the concentration of H₂CN radicals in both combustion and astrophysical processes. The rate constants of H₂CN + H₂CN have been determined by previous experiments, whereas its detailed evolution process and product distribution are still unclear. In this work, by means of quantum chemical and master equation calculations, we for the first time explored theoretically the potential energy surface and kinetics of the H₂CN + H₂CN reaction. At the CCSD(T)/6-311++G(2df,p), CCSD(T)/aug-cc-pVTZ and Gaussian-3 single-point levels based on the B3LYP/6-31++G(d,p) structures, the dominant channel was found to be (R) H₂CN + H₂CN → H₂CNNCH₂ (L1) → r-CH₂NNCH₂ (r1) → N₂ + C₂H₄ (P1) with a zero overall barrier. The calculated rate constants are in agreement with available experiments. Of particular interest, since the formed product involves molecular nitrogen, the H₂CN + H₂CN reaction might have important contribution to the nitrogen-recycling in a number of conflagrant and astrophysical processes.