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

• Published in: Computational and theoretical chemistry 2017-01, Vol.1099, p.140-151
• Main Authors: Sun, Jingyu, Shao, Youxiang, Zhou, Da, Wu, Wenzhong, Yin, Yunhang, Tang, Yizhen, Liu, Jiangyan, Wang, Weidong, Wang, Juan, Chen, Fang, Cheng, Yinfang
• Format: Article
• Language: English
• Subjects: Atmospheric reaction; Crotononitrile; Mechanism; Potential energy surface; Rate constant
• ISSN: 2210-271X
• DOI: 10.1016/j.comptc.2016.11.016

The mechanism and kinetics of O(3P)with crotononitrile reaction have been investigated using the theoretical methods. [Display omitted] •The O(3P)+CH3CHCHCN reaction are important for atmospheric and combustion chemistry.•The mechanism for the reaction of O(3P) with crotononitrile was studied theoretically.•The rate constants were studied by CTST and RRKM theory.•The most important products are CH3 and HCOHCCN. 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.