Formation of nitrosamines and alkyldiazohydroxides in the gas phase: The CH3NH NO reaction revisited

Abstract

Aminyl free radicals of the form RN•H are formed in the photochemical oxidation of primary amines, and their reaction with •NO is an important tropospheric sink. Reaction of the parent methylamidogen radical (CH3N•H) with •NO in the gas phase has been studied using quantum chemical techniques and RRKM theory/master equation based kinetic modeling. Calculations with the G3X-K composite theoretical method indicate that reaction proceeds via exothermic formation of a primary nitrosamine intermediate, CH3NHNO, which can isomerize to an alkyldiazohydroxide, CH3NNOH, and further eliminate water to form diazomethane, CH2NN. Master equation simulations conducted at tropospheric conditions identify t..