Energetics and kinetics of various cyano radical hydrogen abstractions

Abstract

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⁻¹ 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.