Theoretical study for the reaction of CH3CN with O(P3)

The low-lying triplet and singlet potential energy surfaces of the O(P3)+CH3CN reaction have been studied at the G3(MP2)//B3LYP/6-311+G(d,p) level. On the triplet surface, six kinds of pathways are revealed, namely, direct hydrogen abstraction, C-addition/elimination, N-addition/elimination, substitution, insertion, and H-migration. Multichannel Rice–Ramsperger–Kassel–Marcus theory and transition-state theory are employed to calculate the overall and individual rate constants over a wide range of temperatures and pressures. It is predicted that the direct hydrogen abstraction and C-addition/elimination on triplet potential energy surface are dominant pathways. Major predicted end products include CH3+NCO and CH2CN+OH. At atmospheric pressure with Ar and N2 as bath gases, CH3C(O)N (IM1) formed by collisional stabilization is dominated at T<700 K, whereas CH3 and NCO produced by C-addition/elimination pathway are the major products at the temperatures between 800 and 1500 K; the direct hydrogen abstraction ...