A Computational Study of the Reaction of Ground-State Nitrogen Atoms with Chloromethyl Radicals

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 109; no. 29; pp. 6540 - 6548
• Main Authors: Cimas, Alvaro, Rayón, Víctor M, Aschi, Massimiliano, Barrientos, Carmen, Sordo, José A, Largo, Antonio
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 28.07.2005
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0508148

A computational study of the N(4S) + CH2Cl reaction has been carried out. The first step of the reaction is the formation of an initial intermediate (NCH2Cl), which is relatively stable and does not involve any energy barrier. The two most exothermic products are those resulting from the release of a chlorine atom, H2CN + Cl and trans-HCNH + Cl. A kinetic study within the framework of the statistical theories suggests that the kinetically preferred product is also the most exothermic one. This is in contrast with the analogue reaction of nitrogen atoms with CH2F, where the preferred product from both thermodynamic and kinetic points of view is HFCN + H. Therefore, reactions of nitrogen atoms with chloromethyl radicals release chlorine atoms as major products. The rate coefficient for the title reaction is estimated to be about 3.09 × 10-13 cm3 s-1 molecule-1 at 300 K, a value four times smaller than the rate coefficient for its fluorine analogue.