The mechanistic and kinetic investigation on the atmospheric reaction of atomic O(3P) with crotononitrile

Abstract

The mechanism and kinetics for the O(3P)+CH3CHCHCN reaction has been investigated firstly. The BHandHLYP and M05-2X methods were employed to obtain the initial geometries. The triplet/singlet potential energy surfaces (PESs) were constructed with high-level BMC-CCSD method. The conventional transition-state theory (CTST) and multichannel RRKM theory were employed to calculate the total and individual rate constants over a wide range of temperatures under high-pressure limit. Our computed rates agree well with the available experimental results. The yield of IM1 is 0.9–0.5 from 200 to 1000K, and the construction of h-P1(OH+CH2CHCHCN) is 0.42 at 2000K under high-pressure limit. The yields of the predicted decomposition products P1(CH3+HCOHCCN), P2(HCCN+CH3CHO) and P3(H+CH3COHCCN) at 298K and 1 atom are 0.81, 0.07, and 0.09, respectively.