Computational studies of the kinetics of the C+NO and O+CN reactions

Artikel i vetenskaplig tidskrift, 2003

Thermal rate coefficients for the reactions C(3P) + NO(X2Π) → CN(X2Σ+) + O(3P), C(3P) + NO(X2Π) → CO(X1Σ+) + N(2D), and O(3P) + CN(X2Σ+) → CO(X1Σ+) + N(2D) in the temperature range from 5 to 5000 K have been obtained using quasiclassical trajectory calculations. Results are reported for two ab initio potential energy surfaces corresponding to states of 2A‘ and 2A‘ ‘ symmetry. Good agreement between calculated and experimental rate coefficients are obtained for the C + NO reactions for all temperatures, whereas the rate coefficient for the O + CN reaction at room temperature is larger than that found experimentally. The dynamics is considerably different on the two potential energy surfaces with the 2A‘ ‘ giving rate coefficients in better agreement with experiments. The quality of the potential energy surfaces are discussed in the light of new electronic structure calculations including spin−orbit coupling.