Ab initio study of the ClO + NH2 reaction: prediction of the total rate constant and product branching ratios.

摘要: The mechanism for ClO + NH2 has been investigated by ab initio molecular orbital and transition-state theory calculations. species involved have optimized at the B3LYP/6-311+G(3df,2p) level their energies refined single-point calculations with modified Gaussian-2 method, G2M(CC2). Ten stable isomers located a detailed potential energy diagram is provided. rate constants branching ratios low-lying channel products including HCl HNO, Cl NH2O, HOCl 3NH (X3Σ-) are calculated. result shows that formation of HNO dominant below 1000 K; over K, NH2O become dominant. However, unimportant 1500 K. pressure-independent individual total can be expressed as k1(HCl HNO) = 4.7 × 10-8(T-1.08) exp(-129/T), k2(Cl NH2O) 1.7 10-9(T-0.62) exp(-24/T), k3(HOCl NH) 4.8 10-29(T5.11) exp(-1035/T), ktotal 5.0 10-9(T-0.67) exp(-1.2/T), res...