Theoretical Study of ClOO + NO Reaction: Mechanism and Kinetics

Theoretical investigations are performed on mechanism and kinetics of the reaction of halogen peroxy radical ClOO with NO radical. The electronic structure information for both of the singlet and triplet potential energy surfaces (PESs) is obtained at the MP2/6-311 + G(2df) level of theory, and the single-point energies are refined by the CCSD(T)/6-311 + G(2df) level. The rate constants for various product channels of the reaction in the pressure range of 1-7600 Torr are predicted. The main results are as follows: On the singlet surface, the addition-elimination mechanism is the most important. First, the N atom of the NO radical can attack the O atom of the ClOO radical to form an energy-riched intermediate IM1 ClOONOtp (21.3 kcal/mol) barrierlessly, then IM1 could isomerizes to IM2 ClOONOcp (22.1 kcal/mol) via a low energy barrier. Both IM1 and IM2 can dissociate to the primary product P(1) ClNO + (1)O(2) and the secondary product P(2) ClO + NO(2). On the triplet surface, the direct Cl-abstraction reaction is the most feasible pathway. The Cl-abstraction can take place via a van der Waals complex, (3)IM1 ONClOO (4.1 kcal/mol), then it fragments readily to give P(1)’ ClNO + (3)O(2) with a small barrier. The kinetic calculations show that at low temperatures, the singlet bimolecular product P(1) is the primary product, while at high temperatures, the triplet product P(1)’ becomes the primary one; only at high pressures and low temperatures, the unimolecular products IM1 and IM2 can be found with quite small yields. At experimentally measured temperature 213 K, ClNO is the primary product in the whole pressure range, which is consistent with the previous experiment. The present study may be useful for further experimental studies for the title reaction.