Atmospheric reaction pathways of methanimine and nitroxyl: a theoretical study.

The kinetics and mechanisms of atmospheric reaction of methanimine (H2CNH) with nitroxyl on the singlet surface were studied by employing DFT, MP2, and CCSD(T) methods along with the 6-311++G(3df, 3pd) and aug-cc-pVTZ basis sets. Also, thermodynamic parameters and rate constants have been computed in the temperature range of 300–3000 K using conventional transition state theory and RRKM theories at MP2/6-311++G(3df,3pd) level. The results show that seven adducts can be produced. Two of them are highly thermodynamically stable (CH4+N2O and HNCNH+H2O). In kinetic point of view, HCN + HNOH and H2CN + H2NO adducts (due to passing one corresponding low-level transition state) are favorable pathways of title reaction. [ABSTRACT FROM AUTHOR]