Gaseous reaction mechanism between two H(2)CN radicals.

The self-recombination of the methylene amidogen radical (H(2)CN) is known to be fast and should play an important role in determining the concentration of H(2)CN radicals in both combustion and astrophysical processes. The rate constants of H(2)CN + H(2)CN have been determined by previous experiments, whereas its detailed evolution process and product distribution are still unclear. In this work, by means of quantum chemical and master equation calculations, we for the first time explored theoretically the potential energy surface and kinetics of the H(2)CN + H(2)CN reaction.

Theoretical study on reaction mechanism of fulminic acid HCNO with CN radical.

The HCNO + CN reaction is one potentially important process during the NO-reburning process for the reduction of NOx pollutants from fossil fuel combustion emissions. To compare with the recent experimental study, we performed the first theoretical potential energy surface investigation on the mechanism of HCNO + CN at the G3B3 and CCSD(T)/aug-cc-pVTZ levels based on the B3LYP/6-311++G(d,p) structures, covering various entrance, isomerization, and decomposition channels. The results indicate that the most favorable channel is to barrierlessly form the entrance isomer L1c NCCHNO followed by successive ring closure and concerted CC and NO bond rupture to generate the product P1 HCN + NCO.