Hydrazine and its Derivatives: Role on Nitrogen Dioxide Hydrolysis and Ensuing Nucleation in the Atmosphere

Hydrazine (HD) and mono‐methyl hydrazine (MMH), as the compositions of rocket fuels and corrosion inhibitor, have a significant impact on the atmospheric environment. The effects of them on the reaction between NO 2 and H 2 O were investigated theoretically from mechanism and kinetics, and it is expected that they can promote the hydrolysis of NO 2 due to their lower free energy barriers. For the subsequent reaction HNO 3 +HONO+HD/MMH, acid base complex and zwitterionic structure were produced through isomerization. When one or two water molecules were involved in the subsequent reaction, only zwitterionic structure can be found with the lower free energy barrier, and the products were more stable than those without water molecules. To study the atmospheric behavior of HD/MMH, the structures, thermodynamics, interaction forces and temperature dependence of the clusters, which were consisted with HNO 3 and HONO with the base molecules including ammonia, amine and amide, were further calculated, and the results show that the hydrogen bond is the main interaction in the clusters. The global minima remained fixed when the temperature increases from 200 K to 325 K. The forming reactions of the clusters were spontaneous, suggesting that ammonia, amine and amide can promote the nucleation of HNO 3 and HONO molecules.