Energetics and Kinetics of Various Cyano Radical Hydrogen Abstractions

The cyano radical (CN) is an abundant, open-shell molecule found in a variety of environments, including the atmosphere, the interstellar medium and combustion processes. In these environments, it often reacts with small, closed-shell molecules via hydrogen abstraction. Both carbon and nitrogen atoms of the cyano radical are reactive sites, however the carbon is more reactive with reaction barrier heights generally between 2-15 kcal/mol lower than those of the analogous nitrogen. The CN + HX -> HCN/HNC + X, with X = H, CH₃, NH₂, OH, F, SiH₃, PH₂, SH, Cl, C₂H, CN reactions have been studied at a high-level of theory, including CCSD(T)-F12a. Furthermore, kinetics were obtained over the 100-1000 K temperature range, showing excellent agreement with those rate constants that have been determined experimentally.