Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO

doi:10.1016/j.comptc.2019.112644

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	Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO
	Cai, Jie 1; Lu, Yousong 1; Wang, Weina 1; Chen, Long 2; Liu, Fengyi 1; Wang, Wenliang 1
刊名	COMPUTATIONAL AND THEORETICAL CHEMISTRY
	2019-12-15
卷号	1170 页码:8
关键词	Criegee intermediate Methacrolein Reaction mechanism Rate constant Organic acids
ISSN号	2210-271X
DOI	10.1016/j.comptc.2019.112644
通讯作者	Wang, Wenliang(wlwang@snnu.edu.cn)
英文摘要	The comprehensive mechanism and kinetics for CH2OO with methacrolein (CH2 = C(CH3)CHO, MACR) reaction were investigated at the CCSD(T)/6-311 + G(2df,2p)//M06-2X/6-311 +G(2df,2p) level of theory. The results show that three kinds of mechanisms including cycloaddition, oxidation and insertion have been identified. Among them, the cycloaddition of CH2OO adding to C=O bond of MACR is more favorable, which occurs via a deeply submerged barrier leading to the formation of energized secondary ozonide (SOZ). The nascent SOZ mainly further decomposes into methacrylic acid and formaldehyde or formic acid and methacrolein, in which formic acid generation follows stepwise and concerted mechanism involving a catalysis for rearrangement of CH2OO by methacrolein. The calculated rate constant for the title reaction at 300 K using canonical variational transition state theory with small curvature tunneling correction is 1.00 x 10(-12) cm(3) molecule(-1) s(-1), which is close to the experimental value of (4.4 +/- 1.0) x 10(-13) cm(3) molecule(-1) s(-1). The results reveal that the reaction provides a new pathway to produce organic acids. However, the contribution of acids from this reaction is small as its relative lower rate, compared to atmospheric CH2OO loss occurring through the hydrolysis of CH2OO + (H2O)(n) (n = 1-2).
资助项目	National Natural Science Foundation of China[21473108] ; National Natural Science Foundation of China[21873060] ; National Natural Science Foundation of China[21636006] ; Fundamental Research Funds for the Central Universities[GK201901007]
WOS关键词	SECONDARY ORGANIC AEROSOL ; METHYL VINYL KETONE ; GAS-PHASE OZONOLYSIS ; DENSITY FUNCTIONALS ; POTENTIAL SOURCE ; CARBONYL OXIDES ; WATER DIMER ; ISOPRENE ; METHACROLEIN ; ACIDS
WOS研究方向	Chemistry
语种	英语
出版者	ELSEVIER
WOS记录号	WOS:000501413400010
资助机构	National Natural Science Foundation of China ; Fundamental Research Funds for the Central Universities
内容类型	期刊论文
源URL	[http://ir.ieecas.cn/handle/361006/13048]
专题	地球环境研究所_粉尘与环境研究室
通讯作者	Wang, Wenliang
作者单位	1.Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Shaanxi, Peoples R China 2.Chinese Acad Sci, Key Lab Aerosol Chem & Phys, SKLLQG, Inst Earth Environm, Xian 710061, Shaanxi, Peoples R China
推荐引用方式 GB/T 7714	Cai, Jie,Lu, Yousong,Wang, Weina,et al. Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO[J]. COMPUTATIONAL AND THEORETICAL CHEMISTRY,2019,1170:8.
APA	Cai, Jie,Lu, Yousong,Wang, Weina,Chen, Long,Liu, Fengyi,&Wang, Wenliang.(2019).Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO.COMPUTATIONAL AND THEORETICAL CHEMISTRY,1170,8.
MLA	Cai, Jie,et al."Reaction mechanism and kinetics of Criegee intermediate CH2OO with CH2 = C(CH3)CHO".COMPUTATIONAL AND THEORETICAL CHEMISTRY 1170(2019):8.