Ab initio study of the reaction path of the reaction HNCO+CN

HNCO is a convenient photolytic source of NCO and NH radicals for laboratory kinetics studies of elementary reaction1] and plays an important role in the combustion and atmosphere chemistry. It can re- move deleterious compounds rapidly from exhausted ga…

Ab initio study of the reaction path of the reaction HNCO+CN

We report ab initio UMP2 calculations of the reaction of CN with HNCO using 6-311G(d,p) basis sets.The obtained results show that the reaction has two product channels: HNCO+CN→HCN+NCO (1) and HNCO+CN→HNCN+CO (2).Channel (1) is a hydrogen abstraction reaction, which is a concerted process.The calculated potential energy barrier is 20.80 kJ/mol at UMP2(full)/6-311G(d,p) level.In the range of reaction temperature (1000―2100 K), the conventional transition theory rate constant for channel (1) ranges from 0.32×10-11 to 6×9 10-11cm3·mol-1·s-1, which is close to the experimental value.Channel (2) is a stepwise reaction involving an intermediate during the process of reaction.The UMP2(full)/6-311G(d,p) potential energy barrier is 83.42 kJ/mol for the rate-controlling step, which is much higher than that of channel (1).